JP7255182B2 - Negative type photosensitive resin composition, cured film, organic EL display and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a negative photosensitive resin composition, a cured film, an organic EL display, and a method for producing the same.

2. Description of the Related Art In recent years, many products using organic electroluminescence (hereinafter, “EL”) displays have been developed for display devices having thin displays, such as smartphones, tablet PCs, and televisions.

In general, an organic EL display has a transparent electrode such as indium tin oxide (hereinafter referred to as "ITO") on the light extraction side of the light emitting element, and a metal electrode such as an alloy of magnesium and silver on the non-light extraction side of the light emitting element. have. In addition, an insulating layer called a pixel dividing layer is formed between the transparent electrode and the metal electrode in order to divide the pixels of the light emitting element. After forming the pixel division layer, a luminescent material is deposited by vapor deposition through a vapor deposition mask in the region corresponding to the pixel region where the pixel division layer is opened and the underlying transparent electrode or metal electrode is exposed, thereby emitting light. A layer is formed. Transparent electrodes and metal electrodes are generally formed by sputtering. In order to prevent disconnection of the formed transparent electrode or metal electrode, the pixel division layer is required to have a low taper pattern shape. be done.

Further, the organic EL display has a thin film transistor (hereinafter referred to as "TFT") for controlling the light emitting element, and a driving TFT, a switching TFT, and the like are formed. In general, these TFTs are formed as a layered structure positioned further below the transparent electrode or metal electrode underlying the pixel division layer. These TFTs and the steps of the TFT array in which the metal wirings connecting the TFTs are formed degrade the uniformity in the film formation of the transparent electrodes, the metal electrodes, the pixel dividing layer and the light-emitting layer that are subsequently formed. It becomes a factor of deterioration of display characteristics and reliability of the organic EL display. Therefore, after forming the TFT array, it is common to form a TFT flattening layer and/or a TFT protective layer to reduce or smooth the steps caused by the TFT array.

An organic EL display has a self-luminous element that emits light using energy resulting from recombination of electrons injected from a cathode and holes injected from an anode. Therefore, when a substance that inhibits the movement of electrons or holes, a substance that forms an energy level that inhibits recombination of electrons and holes, or the like exists, the emission efficiency of the light-emitting element is reduced or the light-emitting material is deactivated. , etc., leading to shortening of the life of the light-emitting element. Since the pixel division layer is formed at a position adjacent to the light emitting element, outgassing from the pixel division layer and outflow of ion components can be a factor in shortening the life of the organic EL display. Therefore, the pixel division layer is required to have high heat resistance. As a photosensitive resin composition having high heat resistance, a negative photosensitive resin composition using a highly heat-resistant polyimide and an oxime ester photopolymerization initiator is known (see, for example, Patent Document 1). .

Further, since the organic EL display has a self-luminous element, visibility and contrast are lowered due to reflection of external light such as sunlight outdoors. Therefore, a technique for reducing external light reflection is required.

A photosensitive resin composition containing an alkali-soluble polyimide and a colorant is known as a technique for blocking external light and reducing external light reflection (see, for example, Patent Document 2). That is, it is a method of reducing external light reflection by forming a pixel division layer having high heat resistance and light shielding properties using a photosensitive resin composition containing polyimide and a colorant such as a pigment.

JP 2016-191905 A WO2016/158672

From the viewpoint of improving the reliability of organic EL displays, the pixel division layer adjacent to the light emitting element is required to have high heat resistance. Since they are formed in close proximity, high heat resistance is also required. However, when a coloring agent such as a pigment is added to the photosensitive resin composition to impart light-shielding properties, as the content of the coloring agent is increased, ultraviolet rays and the like are blocked during pattern exposure. Sensitivity decreases. Therefore, all of the conventionally known photosensitive resin compositions containing colorants have properties that are not suitable for use as a material for forming a pixel dividing layer, a TFT flattening layer, or a TFT protective layer of an organic EL display. was inadequate. Specifically, any one of the sensitivity, the light shielding property, and the low tapered shape pattern processability was insufficient.

For example, when the light-shielding property of the photosensitive resin composition is improved, the deep portion of the film is side-etched during development because the hardening of the deep portion of the film is insufficient during pattern exposure. As a result, a reverse tapered shape is formed after development, which is a factor that hinders formation of a low tapered pattern. On the other hand, in order to sufficiently harden the film deeply, it is necessary to increase the exposure dose during pattern exposure to promote UV hardening. However, when the exposure amount is high, the film is excessively crosslinked during UV curing, and the reflow property during thermal curing is lowered, resulting in the formation of a highly tapered pattern. Therefore, for example, in a photosensitive resin composition containing an alkali-soluble polyimide and a coloring agent such as a pigment, described in Patent Document 2, it is possible to combine characteristics such as sensitivity, light shielding properties, and low tapered pattern formation. There was a problem of difficulty.

Furthermore, when a highly tapered pattern is formed after development and a low tapered pattern is formed by reflow during heat curing, the bottom of the pattern is also reflowed during heat curing. Therefore, the pattern opening dimension width after heat curing is smaller than the pattern opening dimension width after development, which causes an error in the pixel design of a display device such as an organic EL display. In addition, variations in the width of pattern openings due to reflow during heat curing cause a decrease in panel manufacturing yield. Therefore, there is also the problem that it is difficult to achieve both the formation of a low-tapered pattern and the suppression of changes in the width of pattern openings before and after heat curing. In order to achieve both characteristics, it is necessary to form a pattern with a low taper shape after development, suppress reflow during heat curing, and suppress changes in pattern opening dimension width.

The present invention has been made in view of the above, and an object of the present invention is to achieve high sensitivity, to be able to form a low tapered pattern after development, and to suppress changes in pattern opening dimension width before and after heat curing. It is possible to obtain a negative photosensitive resin composition capable of obtaining a cured film excellent in light shielding properties.

A further object of the present invention is to have high sensitivity, to be able to form a low tapered pattern after development, to be able to suppress changes in pattern opening dimension width before and after heat curing, and to be light-shielding. To provide an excellent cured film and an organic EL display.

（一般式（１１）において、Ｘ^７は、直接結合、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基、又は炭素数６～１５のアリーレン基を表す。Ｘ^７が、直接結合、炭素数１～１０のアルキレン基、又は炭素数４～１０のシクロアルキレン基の場合、Ｒ^２９は、水素、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のハロアルキル基、炭素数１～１０のハロアルコキシ基、炭素数２～１０のアシル基、又はニトロ基を表す。Ｘ^７が、炭素数６～１５のアリーレン基の場合、Ｒ^２９は、水素、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のハロアルキル基、炭素数１～１０のハロアルコキシ基、炭素数４～１０の複素環基、炭素数４～１０の複素環オキシ基、炭素数２～１０のアシル基、又はニトロ基を表す。Ｒ^３０は、水素、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、又は炭素数６～１５のアリール基を表す。ａは、０又は１を表し、ｂは、０～１０の整数を表す。）In order to solve the above-described problems and achieve the above objects, the negative photosensitive resin composition according to one aspect of the present invention comprises (A) an alkali-soluble resin, (C1) a photopolymerization initiator, and (Da) A negative photosensitive resin composition containing a black agent, wherein the (A) alkali-soluble resin is (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) containing one or more types selected from the group consisting of polybenzoxazole precursors (A1) containing a first resin, the (A1-1) polyimide, and the (A1-2) polyimide precursor , the (A1-3) polybenzoxazole, and the (A1-4) polybenzoxazole precursor, one or more types of structural units having a fluorine atom, 10 to 100 mol% of all structural units The (C1) photopolymerization initiator contains (C1-1) an oxime ester photopolymerization initiator, and the (C1-1) oxime ester photopolymerization initiator comprises (I), ( A negative photosensitive resin composition having one or more structures selected from the group consisting of II) and (III).
(I) one or more structures selected from the group consisting of a naphthalenecarbonyl structure, a trimethylbenzoyl structure, a thiophenecarbonyl structure, and a furancarbonyl structure (II) a nitro group, a carbazole structure, and a group represented by general formula (11) (III) a nitro group and one or more structures selected from the group consisting of a fluorene structure, a dibenzofuran structure, a dibenzothiophene structure, a naphthalene structure, a diphenylmethane structure, a diphenylamine structure, a diphenylether structure, and a diphenylsulfide structure;

(In general formula (11), X ⁷ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group ^having 6 to 15 carbon atoms. In the case of a direct bond, an alkylene group having 1 to 10 carbon atoms, or a cycloalkylene group having 4 to 10 carbon atoms, R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, represents an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group, and X ⁷ represents 6 carbon atoms; -15 arylene group, R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. , a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or ^a nitro group. , hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, a represents 0 or 1, b represents 0 to 10 represents an integer.)

A cured film according to one aspect of the present invention is obtained by curing the negative photosensitive resin composition according to the above invention.

In the organic EL display according to one aspect of the present invention, the optical density per 1 μm of the cured film according to the above invention is 0.3 to 5.0, and the cured film comprises a pixel dividing layer, an electrode insulating layer, and a layer, wiring insulating layer, interlayer insulating layer, TFT flattening layer, electrode flattening layer, wiring flattening layer, TFT protective layer, electrode protective layer, wiring protective layer, and gate insulating layer. Prepare as

A method for manufacturing an organic EL display according to one aspect of the present invention is a method for manufacturing an organic EL display according to the above invention, wherein the negative photosensitive resin composition according to the above invention is formed on a substrate. The step of forming a coating film, the step of irradiating the coating film of the negative photosensitive resin composition with actinic radiation through a photomask, developing with an alkaline solution, and the negative photosensitive resin composition and heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.

According to the negative photosensitive resin composition of the present invention, it has high sensitivity, can form a low tapered pattern after development, and can suppress changes in pattern opening dimension width before and after heat curing. It becomes possible to obtain a cured film having excellent light-shielding properties.

Further, according to the cured film, the organic EL display and the manufacturing method thereof according to the present invention, it is possible to form a pattern with high sensitivity and a low taper shape after development, and the change in the width of the pattern opening before and after heat curing is suppressed. It is possible to obtain a cured film excellent in light-shielding properties, and to obtain an organic EL display provided with this cured film.

FIG. 1 is a schematic sectional view illustrating the manufacturing process of steps 1 to 7 in an organic EL display using a cured film of the negative photosensitive resin composition of the present invention. FIG. 2 is a schematic cross-sectional view illustrating the manufacturing process of steps 1 to 13 in a liquid crystal display using a cured film of the negative photosensitive resin composition of the present invention. FIG. 3 is a cross-sectional view showing an example of a cured pattern having a step shape. FIG. 4 is a schematic plan view illustrating the manufacturing process of steps 1 to 4 for the substrate of the organic EL display used for evaluating the light emission characteristics. FIG. 5 is a schematic diagram illustrating a schematic cross section of an organic EL display that does not have a polarizing layer. FIG. 6 is a schematic diagram illustrating the arrangement and dimensions of the light-transmitting portion, the light-shielding portion, and the semi-light-transmitting portion in the halftone photomask used for halftone characteristic evaluation.

The negative photosensitive resin composition of the present invention is a negative photosensitive resin composition containing (A) an alkali-soluble resin, (C1) a photopolymerization initiator, and (Da) a black agent, wherein the (A ) One type of alkali-soluble resin selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor (A1) containing the first resin containing the above, the (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor one or more types selected from the group consisting of groups have a structural unit having a fluorine atom in 10 to 100 mol% of the total structural units, and the (C1) photopolymerization initiator is (C1-1) an oxime ester-based It contains a photopolymerization initiator, and the (C1-1) oxime ester photopolymerization initiator has one or more structures selected from the group consisting of (I), (II), and (III).
(I) one or more structures selected from the group consisting of a naphthalenecarbonyl structure, a trimethylbenzoyl structure, a thiophenecarbonyl structure, and a furancarbonyl structure (II) a nitro group, a carbazole structure, and a group represented by general formula (11) (III) a nitro group and one or more structures selected from the group consisting of a fluorene structure, a dibenzofuran structure, a dibenzothiophene structure, a naphthalene structure, a diphenylmethane structure, a diphenylamine structure, a diphenylether structure, and a diphenylsulfide structure;

(In general formula (11), X ⁷ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group ^having 6 to 15 carbon atoms. In the case of a direct bond, an alkylene group having 1 to 10 carbon atoms, or a cycloalkylene group having 4 to 10 carbon atoms, R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, represents an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group, and X ⁷ represents 6 carbon atoms; -15 arylene group, R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. , a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or ^a nitro group. , hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, a represents 0 or 1, b represents 0 to 10 represents an integer.)

<(A1) First resin>
The negative photosensitive resin composition of the present invention contains at least (A1) the first resin as (A) the alkali-soluble resin. (A1) As the first resin, one type selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor contains more than In the present invention, (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are a single resin or a combination thereof. Any polymer may be used.

(A) As the alkali-soluble resin, from the viewpoint of improving the halftone characteristics, improving the heat resistance of the cured film, and improving the reliability of the light emitting element, (A1) as the first resin, (A1-1) polyimide, ( A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) preferably contains one or more selected from the group consisting of polybenzoxazole precursor, (A1-1) polyimide , and/or (A1-3) more preferably contains polybenzoxazole, and (A1-1) more preferably contains polyimide.

<(A1-1) polyimide and (A1-2) polyimide precursor>
(A1-2) Polyimide precursors include, for example, a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, or a tetracarboxylic acid diester dichloride, and a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. and has a tetracarboxylic acid residue and/or derivative residue thereof and a diamine residue and/or derivative residue thereof. (A1-2) Examples of polyimide precursors include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.

(A1-1) As the polyimide, for example, those obtained by subjecting the above-described polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide to dehydration ring closure by heating or by a reaction using an acid or a base. and have tetracarboxylic acid residues and/or derivative residues thereof and diamine residues and/or derivative residues thereof.

(A1-2) The polyimide precursor is a thermosetting resin, and is thermally cured at a high temperature for dehydration ring closure to form a highly heat-resistant imide bond, thereby obtaining (A1-1) polyimide. Therefore, by including (A1-1) polyimide having a highly heat-resistant imide bond in the negative photosensitive resin composition, the heat resistance of the resulting cured film can be remarkably improved. Therefore, it is suitable for applications where the cured film is required to have high heat resistance. In addition, (A1-2) polyimide precursor is a resin whose heat resistance is improved after dehydration ring closure, so it is used in applications where it is desired to achieve both the properties of the precursor structure before dehydration ring closure and the heat resistance of the cured film. preferred.

In addition, (A1-1) polyimide and (A1-2) polyimide precursor have an imide bond and/or an amide bond as a polar bond. Therefore, when the (D) colorant described later, in particular, the (D1) pigment is contained, these polar bonds strongly interact with the (D1) pigment, so that the dispersion stability of the (D1) pigment is improved. be able to.

The (A1-1) polyimide used in the present invention preferably contains a structural unit represented by the following general formula (1) from the viewpoint of improving the heat resistance of the cured film.

In general formula (1), R ¹ represents a 4- to 10-valent organic group, and R ² represents a 2- to 10-valent organic group. R ³ and R ⁴ each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by general formula (5) or general formula (6). p represents an integer of 0-6 and q represents an integer of 0-8.

R ¹ in general formula (1) represents a tetracarboxylic acid residue and/or a derivative residue thereof, and R ² represents a diamine residue and/or a derivative residue thereof. Tetracarboxylic acid derivatives include tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid activated diesters. Diamine derivatives include diisocyanate compounds or trimethylsilylated diamines.

In general formula (1), R ¹ has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. A 4- to 10-valent organic group is preferred. In addition, R ² is a divalent to decavalent structure having one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. Organic groups are preferred. q is preferably 1-8. The aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms, and may be unsubstituted or substituted.

In general formulas (5) and (6), R ¹⁹ to R ²¹ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or a represents an aryl group. In general formulas (5) and (6), R ¹⁹ to R ²¹ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a Aryl groups are preferred. The alkyl group, acyl group, and aryl group described above may be unsubstituted or substituted.

(A1-1) Polyimide preferably contains a structural unit represented by general formula (1) as a main component, and (A1-1) occupying all structural units in polyimide, represented by general formula (1) The content ratio of the represented structural unit is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol %, the heat resistance of the cured film can be improved.

The (A1-2) polyimide precursor used in the present invention preferably contains a structural unit represented by the following general formula (3) from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development. .

In general formula (3), R ⁹ represents a 4- to 10-valent organic group, and R ¹⁰ represents a 2- to 10-valent organic group. R ¹¹ represents a substituent represented by the general formula (5) or general formula (6) described above, R ¹² represents a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group, and R ¹³ represents a phenolic It represents a hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). t represents an integer of 2 to 8, u represents an integer of 0 to 6, v represents an integer of 0 to 8, and 2≦t+u≦8.

^R9 in general formula (3) represents a tetracarboxylic acid residue and/or a derivative residue thereof, and ^R10 represents a diamine residue and/or a derivative residue thereof. Tetracarboxylic acid derivatives include tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid activated diesters. Diamine derivatives include diisocyanate compounds or trimethylsilylated diamines.

In general formula (3), R ⁹ has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. A 4- to 10-valent organic group is preferred. In addition, R ¹⁰ is a divalent to decavalent structure having one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. Organic groups are preferred. v is preferably 1-8. The aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms, and may be unsubstituted or substituted.

(A1-2) The polyimide precursor preferably contains a structural unit represented by the general formula (3) as a main component, and (A1-2) occupying all structural units in the polyimide precursor, the general formula The content ratio of the structural unit represented by (3) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol %, the resolution can be improved.

(A1-2) As the polyimide precursor, when R ¹¹ in the structural unit represented by general formula (3) is a substituent represented by general formula (5), R ¹⁹ is hydrogen. The unit is called an amic acid structural unit. (A1-2) The amic acid structural unit in the polyimide precursor has a carboxy group as a tetracarboxylic acid residue and/or a derivative residue thereof. The polyimide precursor (A1-2) in which R ¹¹ in the structural unit represented by the general formula (3) consists only of the substituent represented by the general formula (5) and R ¹⁹ is hydrogen is obtained by ( A1-2a) It is called polyamic acid.

(A1-2) As the polyimide precursor, when R ¹¹ in the structural unit represented by general formula (3) is a substituent represented by general formula (5), R ¹⁹ has 1 to 1 carbon atoms A structural unit that is an alkyl group having 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms is referred to as an amide ester structural unit. (A1-2) The amic acid ester structural unit in the polyimide precursor has a carboxylic acid ester group as a group obtained by esterifying a tetracarboxylic acid residue and/or a derivative residue thereof. In addition, R ¹¹ in the structural unit represented by general formula (3) consists only of substituents represented by general formula (5), R ¹⁹ is an alkyl group having 1 to 10 carbon atoms and 2 to 6 carbon atoms. (A1-2) which is an acyl group or an aryl group having 6 to 15 carbon atoms is referred to as (A1-2b) polyamic acid ester.

(A1-2) As the polyimide precursor, the structural unit in the case where R ¹¹ in the structural unit represented by the general formula (3) is a substituent represented by the general formula (6) is an amic acid amide structure called a unit. (A1-2) The amic acid amide structural unit in the polyimide precursor has a carboxylic acid amide group as a group in which a tetracarboxylic acid residue and/or a derivative residue thereof is amidated. In addition, R ¹¹ in the structural unit represented by general formula (3) is (A1-2) polyimide precursor consisting only of substituents represented by general formula (6), (A1-2c) polyamic acid amide It says.

From the viewpoint of improving resolution after development and forming a low-tapered pattern after development, (A1-2) the polyimide precursor includes the amic acid structural unit, and the amic acid ester structural unit and/or the amic acid It preferably contains an amide structural unit. The (A1-2) polyimide precursor containing the amic acid structural unit and the amic acid ester structural unit is referred to as (A1-2-1) polyamic acid partial ester. On the other hand, the (A1-2) polyimide precursor containing the amic acid structural unit and the amic acid amide structural unit is referred to as (A1-2-2) polyamic acid partial amide. The (A1-2) polyimide precursor containing the amic acid structural unit, the amic acid ester structural unit and the amic acid amide structural unit is referred to as (A1-2-3) polyamic acid partial ester amide. These polyimide precursors containing amic acid structural units and amic acid ester structural units and/or amic acid amide structural units have carboxy groups as tetracarboxylic acid residues and/or derivative residues thereof (A1- 2a) It can be synthesized from polyamic acid by esterifying a portion of the carboxy groups and/or amidating a portion of the carboxy groups.

(A1-2) The content ratio of polyamic acid units to all structural units in the polyimide precursor is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 30 mol % or more. When the content ratio is 10 mol % or more, the resolution after development can be improved. On the other hand, the content ratio of polyamic acid units is preferably 60 mol % or less, more preferably 50 mol % or less, and even more preferably 40 mol % or less. When the content is 60 mol % or less, a pattern with a low taper shape can be formed after development.

(A1-2) The total content of polyamic acid ester units and polyamic acid amide units in all structural units in the polyimide precursor is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more. . When the total content ratio is 40 mol % or more, a pattern with a low taper shape can be formed after development. On the other hand, the total content ratio of polyamic acid ester units and polyamic acid amide units is preferably 90 mol % or less, more preferably 80 mol % or less, and even more preferably 70 mol %. When the total content ratio is 90 mol % or less, the resolution after development can be improved.

<(A1-3) Polybenzoxazole and (A1-4) Polybenzoxazole precursor>
(A1-4) The polybenzoxazole precursor is obtained, for example, by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid active diester with a bisaminophenol compound as a diamine. have a dicarboxylic acid residue and/or a derivative residue thereof and a bisaminophenol compound residue and/or a derivative residue thereof. (A1-4) Polybenzoxazole precursors include, for example, polyhydroxyamides.

(A1-3) Polybenzoxazoles include, for example, those obtained by dehydrating and ring-closing a dicarboxylic acid and a bisaminophenol compound as a diamine through a reaction using polyphosphoric acid, and the above-described polyhydroxyamides. , heating, or a reaction with phosphoric anhydride, a base, or a carbodiimide compound, etc., to dehydrate and ring-close the dicarboxylic acid residue and/or its derivative residue, and the bisaminophenol compound residue. group and/or derivative residues thereof.

(A1-4) The polybenzoxazole precursor is a thermosetting resin, and is thermally cured at a high temperature to cause dehydration ring closure to form a highly heat-resistant and rigid benzoxazole ring, and (A1-3) polybenzoxazole An oxazole is obtained. Therefore, by including (A1-3) polybenzoxazole having a highly heat-resistant and rigid benzoxazole ring in the negative photosensitive resin composition, the heat resistance of the resulting cured film can be significantly improved. Therefore, it is suitable for applications where the cured film is required to have high heat resistance. In addition, since the polybenzoxazole precursor (A1-4) is a resin whose heat resistance is improved after dehydration ring closure, it is used in applications where it is desired to achieve both the properties of the precursor structure before dehydration ring closure and the heat resistance of the cured film. etc.

In addition, (A1-3) polybenzoxazole and (A1-4) polybenzoxazole precursor have an oxazole bond and/or an amide bond as a polar bond. Therefore, when the (D) colorant described later, in particular, the (D1) pigment is contained, these polar bonds strongly interact with the (D1) pigment, so that the dispersion stability of the (D1) pigment is improved. be able to.

(A1-3) polybenzoxazole used in the present invention preferably contains a structural unit represented by general formula (2) from the viewpoint of improving the heat resistance of the cured film.

In general formula (2), R ⁵ represents a divalent to decavalent organic group, and R ⁶ represents a tetravalent to decavalent organic group having an aromatic structure. R ⁷ and R ⁸ each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by general formula (5) or general formula (6) described above. r represents an integer of 0-8, and s represents an integer of 0-6.

^R5 in general formula (2) represents a dicarboxylic acid residue and/or a derivative residue thereof, and ^R6 represents a bisaminophenol compound residue and/or a derivative residue thereof. Dicarboxylic acid derivatives include dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.

In general formula (2), R ⁵ has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. Divalent to decavalent organic groups are preferred. Further, R ⁶ is preferably a tetravalent to decavalent organic group having an aromatic structure with 6 to 30 carbon atoms. s is preferably 1-8. The aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms, and may be unsubstituted or substituted.

(A1-3) Polybenzoxazole preferably contains a structural unit represented by general formula (2) as a main component. The content ratio of the structural unit represented by (2) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol %, the heat resistance of the cured film can be improved.

The (A1-4) polybenzoxazole precursor used in the present invention may contain a structural unit represented by the general formula (4) from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development. preferable.

In general formula (4), R ¹⁴ represents a divalent to 10-valent organic group, and R ¹⁵ represents a 4- to 10-valent organic group having an aromatic structure. R ¹⁶ represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6), R ¹⁷ represents a phenolic hydroxyl group, R ¹⁸ represents a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). w represents an integer of 0 to 8, x represents an integer of 2 to 8, y represents an integer of 0 to 6, and 2≦x+y≦8.

^R14 in general formula (4) represents a dicarboxylic acid residue and/or a derivative residue thereof, and ^R15 represents a bisaminophenol compound residue and/or a derivative residue thereof. Dicarboxylic acid derivatives include dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.

In general formula (4), R ¹⁴ has one or more selected from an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. Divalent to decavalent organic groups are preferred. Further, R ¹⁵ is preferably a tetravalent to decavalent organic group having an aromatic structure with 6 to 30 carbon atoms. The aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms, and may be unsubstituted or substituted.

(A1-4) The polybenzoxazole precursor preferably contains a structural unit represented by the general formula (4) as a main component, and (A1-4) all structural units in the polybenzoxazole precursor The content ratio of the structural unit represented by general formula (4) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol %, the resolution can be improved.

<Tetracarboxylic acids, dicarboxylic acids, and derivatives thereof>
Tetracarboxylic acids include, for example, aromatic tetracarboxylic acids, alicyclic tetracarboxylic acids, and aliphatic tetracarboxylic acids. These tetracarboxylic acids may have a heteroatom other than the oxygen atom of the carboxy group.

As the dicarboxylic acid and its derivative in (A1-3) polybenzoxazole and (A1-4) polybenzoxazole precursor, tricarboxylic acid and/or its derivative may be used. Dicarboxylic acids and tricarboxylic acids include, for example, aromatic dicarboxylic acids, aromatic tricarboxylic acids, alicyclic dicarboxylic acids, alicyclic tricarboxylic acids, aliphatic dicarboxylic acids, or aliphatic tricarboxylic acids. These dicarboxylic acids and tricarboxylic acids may have a heteroatom other than the oxygen atom in addition to the oxygen atom of the carboxy group.

Examples of tetracarboxylic acids, dicarboxylic acids, tricarboxylic acids, and derivatives thereof include compounds described in International Publication No. 2017/057281.

<Diamine and its derivative>
Diamines and derivatives thereof include, for example, aromatic diamines, bisaminophenol compounds, alicyclic diamines, alicyclic dihydroxydiamines, aliphatic diamines, or aliphatic dihydroxydiamines. These diamines and derivatives thereof may have heteroatoms in addition to the nitrogen and oxygen atoms of the amino group and derivatives thereof.

Examples of diamines and derivatives thereof include compounds described in International Publication No. 2017/057281.

<Structural Unit Having Fluorine Atom>
(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor, a structural unit having a fluorine atom is contained in an amount of 10 to 100 mol % of all structural units. At least one type selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is a structural unit having a fluorine atom By containing, the transparency can be improved, the sensitivity at the time of exposure can be improved, and a low tapered pattern can be formed after development. In addition, halftone characteristics can be improved. It is presumed that this is because radical curing in the deep part of the film became possible due to the improved transparency of the film. In addition, when the specific oxime ester photopolymerization initiator (C1-1) described later has a group substituted with a halogen, the compatibility between the resin and the initiator can be improved, and the exposure can be performed even in the deep part of the film. This is probably because the UV curing at time proceeds efficiently. In addition, fluorine atoms can impart water repellency to the film surface, which can suppress permeation of the developer into the film surface during alkaline development and suppress side etching by the developer. The term “exposure” as used herein means irradiation with actinic rays (radiation), and examples thereof include irradiation with visible light, ultraviolet rays, electron beams, X-rays, and the like. From the viewpoint of being a commonly used light source, for example, an ultra-high pressure mercury lamp light source capable of irradiating visible light and ultraviolet rays is preferable, and j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) is more preferable. Hereinafter, exposure refers to irradiation with actinic rays (radiation).

In general, when using (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and/or (A1-4) polybenzoxazole precursor, these resins are As the solvent used for dissolution, which will be described later, it is necessary to use a highly polar solvent such as N-methyl-2-pyrrolidone, dimethylsulfoxide, N,N-dimethylformamide, or γ-butyrolactone. However, when the (D) colorant described later, particularly the (D1) pigment is contained, these highly polar solvents strongly interact with the (D1) pigment, so the (A1) first resin, the (A2) ) The effect of improving the dispersion stability by the second resin or (E) the dispersant described later may be insufficient.

(A1-1) a polyimide, (A1-2) a polyimide precursor, (A1-3) a polybenzoxazole, and (A1-4) a structural unit having a fluorine atom or more selected from a polybenzoxazole precursor By containing it, the solubility in a solvent can be improved. Therefore, it is possible to reduce the content of the above-described highly polar solvent or to dissolve these resins without using a highly polar solvent, and (D1) the dispersion stability of the pigment can be improved.

(A1-1) polyimide and / or (A1-2) polyimide precursor contains, as a structural unit having a fluorine atom, a structural unit derived from tetracarboxylic acid having a fluorine atom and / or derived from a derivative thereof A structural unit, or a structural unit derived from a diamine having a fluorine atom and/or a structural unit derived from a derivative thereof may be mentioned.

The structural unit having a fluorine atom contained in (A1-3) polybenzoxazole and/or (A1-4) polybenzoxazole precursor is a structural unit derived from a dicarboxylic acid having a fluorine atom and/or a derivative thereof. or a structural unit derived from a bisaminophenol compound having a fluorine atom and/or a structural unit derived from a derivative thereof.

(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor for all structural units in one or more resins The content ratio of structural units having a fluorine atom is preferably 30 to 100 mol %. The content ratio of structural units having a fluorine atom is more preferably 50 mol % or more, and even more preferably 70 mol % or more. When the content ratio is 30 to 100 mol %, the sensitivity during exposure can be improved.

(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor in at least one resin selected from all carboxylic acids From a tetracarboxylic acid having a fluorine atom, a tetracarboxylic acid derivative having a fluorine atom, a dicarboxylic acid having a fluorine atom, and a dicarboxylic acid derivative having a fluorine atom, accounting for the total number of structural units derived from structural units derived from and derivatives thereof, The content ratio of structural units derived from one or more selected types is preferably 30 to 100 mol %. The content ratio of structural units having a fluorine atom is more preferably 50 mol % or more, and even more preferably 70 mol % or more. When the content ratio is 30 to 100 mol %, the sensitivity during exposure can be improved.

(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) derived from total amine in one or more resins selected from polybenzoxazole precursor selected from a diamine having a fluorine atom, a diamine derivative having a fluorine atom, a bisaminophenol compound having a fluorine atom, and a bisaminophenol compound derivative having a fluorine atom, in the total number of structural units derived from the structural units and derivatives thereof. The content ratio of the structural units derived from one or more types of the compound is preferably 30 to 100 mol%. The content ratio of structural units having a fluorine atom is more preferably 50 mol % or more, and even more preferably 70 mol % or more. When the content ratio is 30 to 100 mol %, the sensitivity during exposure can be improved.

<Structural Unit Derived from Aromatic Carboxylic Acid and its Derivative>
(A1-1) polyimide and/or (A1-2) polyimide precursor preferably contains a structural unit derived from an aromatic carboxylic acid and/or a structural unit derived from a derivative thereof. (A1-1) polyimide and / or (A1-2) polyimide precursor contains a structural unit derived from an aromatic carboxylic acid and / or a structural unit derived from a derivative thereof, the heat resistance of the aromatic group By, the heat resistance of the cured film can be improved. As the aromatic carboxylic acid and its derivative, an aromatic tetracarboxylic acid and/or its derivative are preferred.

(A1-1) polyimide and / or (A1-2) structural units derived from aromatic carboxylic acids in the total number of structural units derived from all carboxylic acids and structural units derived from derivatives thereof in the polyimide precursor and /Or the content ratio of structural units derived from derivatives thereof is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol %, the heat resistance of the cured film can be improved.

(A1-3) polybenzoxazole and/or (A1-4) polybenzoxazole precursor preferably contains a structural unit derived from an aromatic carboxylic acid and/or a structural unit derived from a derivative thereof. (A1-3) polybenzoxazole and/or (A1-4) polybenzoxazole precursor contains a structural unit derived from an aromatic carboxylic acid and/or a structural unit derived from a derivative thereof, thereby obtaining an aromatic The heat resistance of the base can improve the heat resistance of the cured film. As aromatic carboxylic acids and their derivatives, aromatic dicarboxylic acids or aromatic tricarboxylic acids and/or their derivatives are preferred, and aromatic dicarboxylic acids and/or their derivatives are more preferred.

(A1-3) polybenzoxazole and / or (A1-4) polybenzoxazole precursor, the total number of structural units derived from all carboxylic acids and structural units derived from derivatives thereof, derived from aromatic carboxylic acid The content ratio of structural units and/or structural units derived from derivatives thereof is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. When the content ratio is 50 to 100 mol %, the heat resistance of the cured film can be improved.

<Structural Units Derived from Aromatic Amines and Their Derivatives>
At least one selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is derived from an aromatic amine It preferably contains a structural unit and/or a structural unit derived from a derivative thereof. At least one selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is derived from aromatic amine By including a structural unit and/or a structural unit derived from a derivative thereof, the heat resistance of the cured film can be improved due to the heat resistance of the aromatic group. Aromatic amines and their derivatives are preferably aromatic diamines, bisaminophenol compounds, aromatic triamines or trisaminophenol compounds and/or their derivatives, and aromatic diamines or bisaminophenol compounds and/or them are more preferred.

(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) derived from total amine in one or more resins selected from polybenzoxazole precursor The content ratio of structural units derived from aromatic amines and/or structural units derived from derivatives thereof in the total of structural units derived from structural units and derivatives thereof is preferably 50 to 100 mol%, and 60 to 100 mol%. is more preferred, and 70 to 100 mol % is even more preferred. When the content ratio is 50 to 100 mol %, the heat resistance of the cured film can be improved.

<Diamine having a silyl group or a siloxane bond, and a structural unit derived from a derivative thereof>
(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor, a silyl group or a siloxane bond It is preferable to contain a structural unit derived from a diamine and/or a structural unit derived from a derivative thereof. (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursors have a silyl group or a siloxane bond. By containing a structural unit derived from a diamine having and / or a structural unit derived from a derivative thereof, the interaction at the interface between the cured film of the negative photosensitive resin composition and the underlying substrate increases, and the underlying substrate and and the chemical resistance of the cured film can be improved.

<Structural unit derived from amine having oxyalkylene structure and derivative thereof>
(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor is an amine having an oxyalkylene structure It preferably contains a structural unit derived from and/or a structural unit derived from a derivative thereof. (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor is an amine having an oxyalkylene structure By containing a structural unit derived from and / or a structural unit derived from a derivative thereof, it is possible to obtain a cured film with a low taper pattern shape, and mechanical properties of the cured film and pattern processability with an alkaline developer can be improved.

<Terminal blocking agent>
(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor, the terminal of the resin is monoamine , a dicarboxylic acid anhydride, a monocarboxylic acid, a monocarboxylic acid chloride, or a monocarboxylic acid active ester. By sealing the ends of the resin with a terminal blocking agent, (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzo The storage stability of the coating liquid of the resin composition containing one or more selected from oxazole precursors can be improved.

(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and/or (A1-4) various carboxylic acids or amines occupying in polybenzoxazole precursor, and their The content ratio of structural units derived from derivatives can be determined by combining ¹ H-NMR, ¹³ C-NMR, ¹⁵ N-NMR, IR, TOF-MS, elemental analysis, ash measurement, and the like.

<Introduction of Ethylenically Unsaturated Double Bond Group>
(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor, ethylenically unsaturated double It is preferred to have a binding group. It is also preferable to introduce an ethylenically unsaturated double bond group into the side chain of these resins by a reaction for introducing an ethylenically unsaturated double bond group. By having an ethylenically unsaturated double bond group, a low tapered pattern can be formed after development.

(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more selected from polybenzoxazole precursor, some of which they have Also preferred are those obtained by reacting a phenolic hydroxyl group and/or a carboxyl group with a compound having an ethylenically unsaturated double bond group. By the reaction described above, it becomes possible to introduce an ethylenically unsaturated double bond group into the side chain of the resin.

As the compound having an ethylenically unsaturated double bond group, an electrophilic compound having an ethylenically unsaturated double bond group is preferable from the viewpoint of reactivity. Examples of electrophilic compounds include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thioketone compounds, acetate compounds, carboxylic acid chlorides, carboxylic acid anhydrides, and carboxylic acid active ester compounds. , carboxylic acid compounds, halogenated alkyl compounds, alkyl azide compounds, triflate alkyl compounds, mesylate alkyl compounds, tosylate alkyl compounds, or alkyl cyanide compounds. An isocyanate compound, an epoxy compound, an aldehyde compound, a ketone compound, or a carboxylic acid anhydride is preferred, and an isocyanate compound or an epoxy compound is more preferred.

<Physical Properties of (A1-1) Polyimide, (A1-2) Polyimide Precursor, (A1-3) Polybenzoxazole, and (A1-4) Polybenzoxazole Precursor>
(A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) one or more weight-average molecular weights selected from polybenzoxazole precursor (hereinafter referred to as " Mw”) is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more in terms of polystyrene measured by gel permeation chromatography (hereinafter “GPC”). The resolution after development can be improved as Mw is 1,000 or more. On the other hand, Mw is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 100,000 or less. When Mw is 500,000 or less, the leveling property during coating and the pattern workability with an alkaline developer can be improved.

Further, the number average molecular weight (hereinafter referred to as "Mn") is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more in terms of polystyrene measured by GPC. When Mn is 1,000 or more, the resolution after development can be improved. On the other hand, Mn is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 100,000 or less. When the Mn is 500,000 or less, leveling properties during coating and pattern processability with an alkaline developer can be improved.

Mw and Mn of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are determined by GPC, light scattering method, or X It can be easily measured as a polystyrene-equivalent value by a linear small-angle scattering method or the like. (A1-1) polyimide, (A1-2) polyimide precursor (A1-3) polybenzoxazole, and (A1-4) repeating number n of structural units in polybenzoxazole precursor is the molecular weight of the structural unit When M and the weight average molecular weight of the resin are Mw, n=Mw/M.

(A1-1) polyimide and (A1-2) polyimide precursor can be synthesized by a known method. For example, in a polar solvent such as N-methyl-2-pyrrolidone, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at 80 to 200°C, or , tetracarboxylic dianhydride (partially replaced with a terminal blocker dicarboxylic anhydride, monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester) and diamine at 80 to 200 ° C. A reaction method and the like can be mentioned.

(A1-3) polybenzoxazole and (A1-4) polybenzoxazole precursor can be synthesized by a known method. For example, in a polar solvent such as N-methyl-2-pyrrolidone, a method of reacting a dicarboxylic acid active diester and a bisaminophenol compound (partially replaced with a monoamine terminal blocker) at 80 to 250°C. , or a dicarboxylic acid active diester (partially replaced with a terminal blocker dicarboxylic anhydride, monocarboxylic acid, monocarboxylic acid chloride, or monocarboxylic acid active ester) and a bisaminophenol compound, 80 A method of reacting at up to 250° C. may be mentioned.

<(A2) Second resin>
The negative photosensitive resin composition of the present invention preferably contains (A2) a second resin as (A) an alkali-soluble resin. (A2) As the second resin, (A2-1) polysiloxane, (A2-2) polycyclic side chain-containing resin, ( A2-3) Acid-modified epoxy resin and (A2-4) It is preferable to contain one or more selected from acrylic resin. In the present invention, (A2-1) polysiloxane, (A2-2) polycyclic side chain-containing resin, (A2-3) acid-modified epoxy resin, and (A2-4) acrylic resin are single resins or may be any of the copolymers.

(A) As the alkali-soluble resin, (A2) As the second resin, (A2-1) polysiloxane from the viewpoint of improving the halftone characteristics, improving the sensitivity at the time of exposure, and reducing the taper by controlling the pattern shape after development. , (A2-2) polycyclic side chain-containing resin, (A2-3) acid-modified epoxy resin, and (A2-4) preferably contains one or more selected from the group consisting of acrylic resin, (A2- 1) polysiloxane, (A2-2) polycyclic side chain-containing resin, and (A2-3) more preferably contains one or more selected from the group consisting of acid-modified epoxy resin, (A2-1) poly It further preferably contains siloxane and/or (A2-2) polycyclic side chain-containing resin, and particularly preferably contains (A2-1) polysiloxane. In addition, by containing (A2-1) polysiloxane, it is possible to form a pattern with a low taper shape after heat curing, and to suppress a change in the width of the pattern opening before and after heat curing.

<(A2-1) Polysiloxane>
Polysiloxane (A2-1) used in the present invention is, for example, one or more selected from trifunctional organosilane, tetrafunctional organosilane, bifunctional organosilane, and monofunctional organosilane, which is hydrolyzed and dehydrated and condensed. polysiloxane obtained by

(A2-1) Polysiloxane is a thermosetting resin, and is thermally cured at a high temperature for dehydration condensation to form a highly heat-resistant siloxane bond (Si—O). Therefore, by including (A2-1) polysiloxane having a highly heat-resistant siloxane bond in the negative photosensitive resin composition, the heat resistance of the resulting cured film can be improved. Moreover, since it is a resin whose heat resistance is improved after dehydration condensation, it is suitable for applications where it is desired to achieve both the properties before dehydration condensation and the heat resistance of the cured film.

In addition, (A2-1) polysiloxane has a silanol group as a reactive group. Therefore, when the (D1) pigment is contained as the (D) colorant described later, the silanol group can interact and/or bond with the surface of the (D1) pigment, and the (D1) pigment It is possible to interact with and/or bind to surface modifying groups. Therefore, the dispersion stability of the (D1) pigment can be improved.

<Trifunctional Organosilane Unit, Tetrafunctional Organosilane Unit, Bifunctional Organosilane Unit, and Monofunctional Organosilane Unit>
The (A2-1) polysiloxane used in the present invention preferably contains a trifunctional organosilane unit and/or a tetrafunctional organosilane unit from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development. . As the trifunctional organosilane, an organosilane unit represented by general formula (7) is preferred. As the tetrafunctional organosilane unit, an organosilane unit represented by general formula (8) is preferred. In addition, from the viewpoint of reducing the taper of the pattern shape and improving the mechanical properties of the cured film, it may contain a bifunctional organosilane unit. As the bifunctional organosilane, an organosilane unit represented by general formula (9) is preferred. Moreover, from the viewpoint of improving the storage stability of the coating liquid of the resin composition, it may contain a monofunctional organosilane unit. As the monofunctional organosilane unit, an organosilane unit represented by general formula (10) is preferred.

In general formulas (7) to (10), R ²² to R ²⁷ each independently represent hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. In general formulas (7) to (10), R ²² to R ²⁷ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a An alkenyl group or an aryl group having 6 to 15 carbon atoms is preferred. The alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups described above may have heteroatoms and may be unsubstituted or substituted.

Examples of organosilanes having an organosilane unit represented by general formula (7), general formula (8), general formula (9), or general formula (10) include those described in International Publication No. 2017/057281. compound.

(A2-1) The content ratio of the organosilane unit represented by the general formula (7) in the polysiloxane is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, more preferably 70 to 100 mol, in terms of Si atomic mol ratio. % is more preferred. When the content ratio is 50 to 100 mol %, the heat resistance of the cured film can be improved. As the organosilane unit represented by the general formula (7), an organosilane unit having an epoxy group is preferred. (A2-1) When the polysiloxane contains the organosilane unit having an epoxy group, it is possible to improve the pattern processability during alkali development and the sensitivity during exposure.

(A2-1) The content ratio of the organosilane unit represented by the general formula (8) in the polysiloxane is preferably 0 to 40 mol%, more preferably 0 to 30 mol%, more preferably 0 to 20 mol, in terms of Si atomic mol ratio. % is more preferred. When the content ratio is 0 to 40 mol %, it is possible to improve the pattern processability during alkali development, improve the sensitivity during exposure, and improve the heat resistance of the cured film. In addition, a pattern with a low taper shape can be formed after development, and a change in pattern opening dimension width before and after heat curing can be suppressed.

(A2-1) The content ratio of the organosilane unit represented by the general formula (9) in the polysiloxane is preferably 0 to 60 mol%, more preferably 0 to 50 mol%, and more preferably 0 to 40 mol, in terms of Si atom mol ratio. % is more preferred. When the content ratio is 0 to 60 mol %, the heat resistance of the cured film and the resolution after development can be improved.

(A2-1) The content ratio of the organosilane unit represented by the general formula (10) in the polysiloxane is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, more preferably 0 to 5 mol, in terms of Si atomic mol ratio. % is more preferred. When the content ratio is 0 to 20 mol %, the heat resistance of the cured film can be improved.

The (A2-1) polysiloxane used in the present invention includes an organosilane represented by the general formula (7a), an organosilane represented by the general formula (8a), and an organosilane represented by the general formula (9a). , and organosilanes represented by the general formula (10a) are preferably polysiloxanes (A2-1) obtained by hydrolyzing and dehydrating condensation.

In general formulas (7a) to (10a), R ²² to R ²⁷ each independently represent hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and R ¹¹⁵ to R ¹²⁴ each independently represents hydrogen, an alkyl group, an acyl group, or an aryl group. In general formulas (7a) to (10a), R ²² to R ²⁷ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a An alkenyl group or an aryl group having 6 to 15 carbon atoms is preferred. R ¹¹⁵ to R ¹²⁴ are each independently preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. The alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and acyl groups described above may have heteroatoms and may be unsubstituted or substituted.

(A2-1) In polysiloxane, an organosilane unit represented by general formula (7), an organosilane unit represented by general formula (8), an organosilane unit represented by general formula (9), and general The organosilane units represented by formula (10) may be arranged either regularly or irregularly. Regular arrangements include, for example, alternating copolymerization, periodic copolymerization, block copolymerization, or graft copolymerization. Irregular sequences include, for example, random copolymerization.

(A2-1) In the polysiloxane, the organosilane unit represented by the general formula (7), the organosilane unit represented by the general formula (8), the organosilane unit represented by the general formula (9), And the organosilane unit represented by general formula (10) may be arranged two-dimensionally or three-dimensionally. A two-dimensional arrangement includes, for example, a linear arrangement. Examples of the three-dimensional array include a ladder-like, cage-like, or mesh-like arrangement.

<Organosilane Unit Having Aromatic Group>
(A2-1) polysiloxane used in the present invention preferably contains an organosilane unit having an aromatic group. Such (A2-1) polysiloxane is an organosilane having an aromatic group-containing organosilane unit represented by general formula (7), general formula (9), or general formula (10). It is preferably obtained using (A2-1) When the polysiloxane contains an organosilane unit having an aromatic group, the heat resistance of the aromatic group can improve the heat resistance of the cured film.

Further, as a (D) colorant described later, especially when (D1) pigment is contained, (A2-1) polysiloxane contains an organosilane unit having an aromatic group, so that the steric hindrance of the aromatic group , (D1) can improve the dispersion stability of the pigment. Furthermore, when the (D1) pigment is (D1-1) an organic pigment, the aromatic group in (A2-1) polysiloxane interacts with the aromatic group of (D1-1) the organic pigment, so (D1 -1) It is possible to improve the dispersion stability of the organic pigment.

(A2-1) The content ratio of the organosilane unit having an aromatic group in the polysiloxane is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more in terms of Si atom mol ratio. When the content ratio is 5 mol % or more, the heat resistance of the cured film can be improved. On the other hand, the content ratio is preferably 80 mol % or less, more preferably 75 mol % or less, and even more preferably 70 mol % or less. If the content ratio is 80 mol % or less, pattern workability with an alkaline developer can be improved. In particular, the Si atom mol ratio derived from the organosilane unit represented by general formula (7), general formula (9), or general formula (10) and having an aromatic group is 5 mol% or more and 80 mol% or less. is preferred.

(A2-1) The content ratio of various organosilane units in polysiloxane can be determined by combining ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis, and ash content measurement. can be asked for.

<(A2-1) Physical properties of polysiloxane>
The Mw of (A2-1) polysiloxane used in the present invention is preferably 500 or more, more preferably 700 or more, and even more preferably 1,000 or more in terms of polystyrene measured by GPC. The resolution after development can be improved as Mw is 500 or more. On the other hand, Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less. When the Mw is 100,000 or less, leveling properties during coating and pattern processability with an alkaline developer can be improved.

(A2-1) Polysiloxane can be synthesized by a known method. For example, a method of hydrolyzing an organosilane in a reaction solvent and subjecting it to dehydration condensation may be used. As a method of hydrolyzing and dehydrating condensation of organosilane, for example, a mixture containing organosilane is added with a reaction solvent, water, and optionally a catalyst, and the mixture is heated at 50 to 150°C, preferably 90 to 130°C. , a method of heating and stirring for about 0.5 to 100 hours, and the like. During heating and stirring, if necessary, hydrolysis by-products (alcohol such as methanol) and condensation by-products (water) may be removed by distillation.

<(A2-2) Polycyclic Side Chain-Containing Resin>
Examples of the (A2-2) polycyclic side chain-containing resin used in the present invention include the following polycyclic side chain-containing resins (I) to (IV).
(I) A polycyclic side chain-containing resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound and a polyfunctional carboxylic acid anhydride with an epoxy compound.
(II) A polycyclic side chain-containing resin obtained by reacting a polyfunctional carboxylic acid anhydride with a compound obtained by reacting a polyfunctional phenol compound and an epoxy compound.
(III) A polycyclic side chain-containing resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound and a polyfunctional carboxylic acid compound with an epoxy compound.
(IV) A polycyclic side chain-containing resin obtained by reacting a polyfunctional carboxylic acid anhydride with a compound obtained by reacting a polyfunctional epoxy compound and a carboxylic acid compound.

Phenolic compounds, epoxy compounds, carboxylic acid anhydrides, and carboxylic acid compounds include, for example, compounds described in International Publication No. 2017/057281.

(A2-2) The polycyclic side chain-containing resin is a thermosetting resin and has a structure in which a main chain and a bulky side chain are connected by one atom. It has a cyclic structure such as a fluorene ring. Therefore, by including (A2-2) a polycyclic side chain-containing resin having a highly heat-resistant and rigid cyclic structure such as a fluorene ring in the negative photosensitive resin composition, the heat resistance of the resulting cured film is improved. can be made Therefore, it is suitable for applications where the cured film is required to have heat resistance.

The (A2-2) polycyclic side chain-containing resin used in the present invention preferably has an ethylenically unsaturated double bond group. By incorporating the (A2-2) polycyclic side chain-containing resin having an ethylenically unsaturated double bond group into the negative photosensitive resin composition, the sensitivity during exposure can be improved. In addition, since the three-dimensional crosslinked structure to be formed is mainly composed of an alicyclic structure or an aliphatic structure, the softening point of the resin is suppressed from increasing, and a pattern shape with a low taper can be obtained. The mechanical properties of the resulting cured film can be improved. Therefore, it is suitable when the cured film is used for applications requiring mechanical properties.

As the (A2-2) polycyclic side chain-containing resin used in the present invention, from the viewpoint of improving the heat resistance of the cured film, the structural unit represented by the general formula (47), the structural unit represented by the general formula (48) It preferably contains one or more selected from structural units, structural units represented by general formula (49), and structural units represented by general formula (50). In addition, the (A2-2) polycyclic side chain-containing resin used in the present invention has one of the main chain, the side chain, and the end from the viewpoint of improving the sensitivity during exposure and improving the mechanical properties of the cured film. Above all, it is preferable to contain an ethylenically unsaturated double bond group.

In general formulas (47) to (50), X ⁶⁹ , X ⁷⁰ , X ⁷² , X ⁷³ , X ⁷⁵ , X ⁷⁶ , X ⁷⁸ and X ⁷⁹ each independently represent a monocyclic or condensed polycyclic represents a hydrocarbon ring. X ⁷¹ , X ⁷⁴ , X ⁷⁷ and X ⁸⁰ each independently represent a divalent to decavalent organic group of a carboxylic acid residue and/or derivative residue thereof. W ¹ to W ⁴ each independently represent an organic group having two or more aromatic groups. R ¹⁶⁰ to R ¹⁶⁷ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ¹⁷⁰ to R ¹⁷⁵ , R ¹⁷⁷ and R ¹⁷⁸ each independently represent hydrogen or ethylenically unsaturated Represents an organic group having a double bond group. R ¹⁷⁶ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. a, b, c, d, e, f, g, and h each independently represent an integer of 0 to 10; α, β, γ, and δ each independently represent 0 or 1; show.

In general formulas (47) to (50), X ⁶⁹ , X ⁷⁰ , X ⁷² , X ⁷³ , X ⁷⁵ , X ⁷⁶ , X ⁷⁸ and X ⁷⁹ each independently has 6 to 15 carbon atoms and 2 to A decavalent, monocyclic or condensed polycyclic hydrocarbon ring is preferred. X ⁷¹ , X ⁷⁴ , X ⁷⁷ and X ⁸⁰ each independently represent an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. Divalent to decavalent organic groups having one or more selected from group structures are preferred. Further, W ¹ to W ⁴ are each independently preferably a substituent represented by any one of general formulas (51) to (56). Further, R ¹⁷⁰ to R ¹⁷⁵ , R ¹⁷⁷ and R ¹⁷⁸ are each independently preferably a substituent represented by general formula (57). The above alkyl group, aliphatic structure, alicyclic structure, aromatic structure, monocyclic or condensed polycyclic aromatic hydrocarbon ring, and organic group having an ethylenically unsaturated double bond group are hetero It may have atoms and may be unsubstituted or substituted.

In general formulas (51) to (56), R ¹⁷⁹ to R ¹⁸² , R ¹⁸⁵ and R ¹⁸⁸ each independently represent an alkyl group having 1 to 10 carbon atoms. R ¹⁸³ , R ¹⁸⁴ , R ¹⁸⁶ , R ¹⁸⁷ , R ¹⁸⁹ , R ¹⁹¹ and R ¹⁹³ to R ¹⁹⁶ are each independently hydrogen, alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 4 to 10 carbon atoms group, or an aryl group having 6 to 15 carbon atoms. R ¹⁹⁰ and R ¹⁹² each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, ^a cycloalkyl group having 4 to 10 carbon atoms, or ^an aryl group having 6 to 15 carbon atoms; may form a ring. Examples of the ring formed by R ¹⁹⁰ and R ¹⁹² include a benzene ring and a cyclohexane ring. At least one of R ¹⁸³ and R ¹⁸⁴ is an aryl group having 6 to 15 carbon atoms. At least one of R ¹⁸⁶ and R ¹⁸⁷ is an aryl group having 6 to 15 carbon atoms. At least one of R ¹⁸⁹ and R ¹⁹⁰ is an aryl group having 6 to 15 carbon atoms, at least one of R ¹⁹¹ and R ¹⁹² is an aryl group having 6 to 15 carbon atoms, and R ¹⁹⁰ and R ¹⁹² A ring may be formed. At least one of R ¹⁹³ and R ¹⁹⁴ is an aryl group having 6 to 15 carbon atoms, and at least one of R ¹⁹⁵ and R ¹⁹⁶ is an aryl group having 6 to 15 carbon atoms. i, j, k, l, m, and n each independently represent an integer of 0 to 4; In general formulas (51) to (56), R ¹⁹⁰ and R ¹⁹² are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or 6 to 10 carbon atoms. is preferred, and the ring formed by R ¹⁹⁰ and R ¹⁹² is preferably a benzene ring. The alkyl group, cycloalkyl group, and aryl group described above may be unsubstituted or substituted.

In the general formula (57), X ⁸¹ represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms, and X ⁸² represents a direct It represents a bond or an arylene chain with 6 to 15 carbon atoms. R ¹⁹⁷ represents a vinyl group, an aryl group, or a (meth)acryl group. In general formula (57), X ⁸¹ is preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. Also, X ⁸² is preferably a direct bond or an arylene chain having 6 to 10 carbon atoms. The alkylene chain, cycloalkylene chain, arylene chain, vinyl group, aryl group, and (meth)acryl group described above may be unsubstituted or substituted.

<One or more selected from tetracarboxylic acids having aromatic group carboxylic acids and derivatives thereof, tetracarboxylic acid dianhydrides having aromatic groups, tricarboxylic acids having aromatic groups, and dicarboxylic acids having aromatic groups Derived Structural Unit>
The (A2-2) polycyclic side chain-containing resin used in the present invention preferably contains a structural unit derived from an aromatic group carboxylic acid or a derivative thereof. (A2-2) The polycyclic side chain-containing resin contains a structural unit derived from an aromatic group carboxylic acid or a derivative thereof, whereby the heat resistance of the aromatic group can improve the heat resistance of the cured film. . The aromatic carboxylic acid and its derivative are selected from tetracarboxylic acid having an aromatic group, tetracarboxylic acid dianhydride having an aromatic group, tricarboxylic acid having an aromatic group, and dicarboxylic acid having an aromatic group. One or more types are preferred.

In addition, when (D1) a pigment is contained as a (D) colorant described later, (A2-2) a polycyclic side chain-containing resin containing a structural unit derived from an aromatic carboxylic acid and a derivative thereof. , the steric hindrance of the aromatic group can improve the dispersion stability of the (D1) pigment. Further, when the (D1) pigment is (D1-1) an organic pigment, the aromatic group in (A2-2) the polycyclic side chain-containing resin interacts with the aromatic group of (D1-1) the organic pigment. Therefore, (D1-1) the dispersion stability of the organic pigment can be improved.

Aromatic carboxylic acids and derivatives thereof include compounds contained in the above-mentioned aromatic tetracarboxylic acids and/or derivatives thereof, aromatic tricarboxylic acids and/or derivatives thereof, or aromatic dicarboxylic acids and/or derivatives thereof. is mentioned.

(A2-2) Containment of structural units derived from an aromatic carboxylic acid and/or derivatives thereof in all structural units derived from tetracarboxylic acids, all dicarboxylic acids, and derivatives thereof in the polycyclic side chain-containing resin The ratio is preferably 10-100 mol %, more preferably 20-100 mol %, and even more preferably 30-100 mol %. When the content ratio is 10 to 100 mol %, the heat resistance of the cured film can be improved.

<Acidic group derived from carboxylic acid and its derivative>
The (A2-2) polycyclic side chain-containing resin used in the present invention contains a structural unit derived from a carboxylic acid and a derivative thereof, and (A2-2) the polycyclic side chain-containing resin has an acidic group. is preferred. (A2-2) The polycyclic side chain-containing resin having an acidic group can improve the pattern processability with an alkaline developer and the resolution after development.

As the acidic group, a group exhibiting an acidity of less than pH 6 is preferred. Examples of groups exhibiting acidity of less than pH 6 include a carboxy group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, or a hydroxyimide group. A carboxy group, a carboxylic anhydride group, or a phenolic hydroxyl group is preferred, and a carboxy group or a carboxylic anhydride group is more preferred, from the viewpoint of improving pattern processability with an alkaline developer and improving resolution after development.

(A2-2) The content ratio of structural units derived from various monomer components in the polycyclic side chain-containing resin is ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, and elemental analysis. It can be obtained by combining the method and ash content measurement.

<Specific examples of (A2-2) polycyclic side chain-containing resin>
Examples of (A2-2) polycyclic side chain-containing resins used in the present invention include "ADEKA ARKLS" (registered trademark) WR-101 or WR-301 (both of which are manufactured by ADEKA), OGSOL (registered Trademark) CR-1030, CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6, CR-TR7, CR-TR8, CR-TR9 , or CR-TR10 (both of which are manufactured by Osaka Gas Chemicals), or TR-B201 or TR-B202 (both of which are manufactured by TRONLY).

<(A2-2) Physical properties of polycyclic side chain-containing resin>
The Mw of the (A2-2) polycyclic side chain-containing resin used in the present invention is preferably 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more in terms of polystyrene measured by GPC. . The resolution after development can be improved as Mw is 500 or more. On the other hand, Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less. When the Mw is 100,000 or less, leveling properties during coating and pattern processability with an alkaline developer can be improved.

<(A2-3) Acid-modified epoxy resin>
The (A2-3) acid-modified epoxy resin used in the present invention includes, for example, the following acid-modified epoxy resins (I) to (VI).
(I) An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional phenol compound and a polyfunctional carboxylic acid anhydride.
(II) Acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound and an epoxy compound with a polyfunctional carboxylic acid anhydride.
(III) An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional alcohol compound and a polyfunctional carboxylic acid anhydride.
(IV) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional alcohol compound and an epoxy compound with a polyfunctional carboxylic acid anhydride.
(V) An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional epoxy compound and a polyfunctional carboxylic acid compound.
(VI) An acid-modified epoxy resin obtained by reacting a polyfunctional carboxylic acid anhydride with a compound obtained by reacting a polyfunctional epoxy compound and a carboxylic acid compound.

Phenolic compounds, alcohol compounds, epoxy compounds, carboxylic acid anhydrides, and carboxylic acid compounds include, for example, compounds described in International Publication No. 2017/057281.

(A2-3) The acid-modified epoxy resin is a thermosetting resin and has a highly heat-resistant aromatic cyclic structure in the epoxy resin skeleton of the main chain. Therefore, by including (A2-3) the acid-modified epoxy resin in the resin composition, the heat resistance of the resulting cured film can be improved. Therefore, it is suitable for applications where the cured film is required to have heat resistance.

The (A2-3) acid-modified epoxy resin used in the present invention preferably has an ethylenically unsaturated double bond group. By including the (A2-3) acid-modified epoxy resin having an ethylenically unsaturated double bond group in the resin composition, the sensitivity during exposure can be improved. In addition, since the three-dimensional crosslinked structure to be formed is mainly composed of an alicyclic structure or an aliphatic structure, the softening point of the resin is suppressed from increasing, and a pattern shape with a low taper can be obtained. The mechanical properties of the resulting cured film can be improved. Therefore, it is suitable when the cured film is used for applications requiring mechanical properties.

The (A2-3) acid-modified epoxy resin used in the present invention has a carboxy group and/or a carboxylic acid anhydride group as an alkali-soluble group. By having a carboxyl group and/or a carboxylic anhydride group, resolution after development can be improved.

As the acid-modified epoxy resin (A2-3) used in the present invention, from the viewpoint of improving the heat resistance of the cured film, a structural unit represented by the general formula (35) and a structural unit represented by the general formula (36) , a structural unit represented by the general formula (37), a structural unit represented by the general formula (38), a structural unit represented by the general formula (41), a structural unit represented by the general formula (42), and It is preferable to contain one or more types selected from structural units represented by general formula (43). In addition, the acid-modified epoxy resin (A2-3) used in the present invention has, from the viewpoint of improving sensitivity during exposure and improving mechanical properties of a cured film, at least one of the main chain, the side chain, and the end, It preferably has an ethylenically unsaturated double bond group.

In general formulas (35) to (38), X ⁵¹ to X ⁵⁴ each independently represent an aliphatic structure having 1 to 6 carbon atoms. Z ⁵³ represents an aromatic structure with 10-25 and 3-16 carbon atoms. R ⁷¹ to R ⁷⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ⁷⁶ and R ⁷⁷ are Each independently represents an alkyl group having 1 to 10 carbon atoms, and R ⁷⁸ to R ⁸² each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or represents an aryl group having 6 to 15 carbon atoms, and R ⁸³ to R ⁸⁸ each independently represents a substituent represented by general formula (39). a, b, c, d, and e each independently represent an integer of 0 to 10, f represents an integer of 0 to 8, g represents an integer of 0 to 6, h, i , j, and k each independently represents an integer of 0 to 3, and l represents an integer of 0 to 4. The alkyl groups, cycloalkyl groups, aryl groups, aliphatic structures, and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.

The aromatic structure of Z ⁵³ in general formula (38) contains one or more selected from the group consisting of terphenyl structure, naphthalene structure, anthracene structure and fluorene structure. Other aromatic structures of Z ⁵³ in general formula (38) include, for example, 1,2,3,4-tetrahydronaphthalene structure, 2,2-diphenylpropane structure, diphenylether structure, diphenylketone structure or diphenylsulfone structure.

In general formula (39), X ⁵⁵ represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. R ⁸⁹ to R ⁹¹ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ⁹² represents hydrogen or a substituent represented by general formula (40). In general formula (39), R ⁸⁹ and R ⁹⁰ are each independently preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen. R ⁹¹ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a methyl group. In general formula (40), X ⁵⁶ represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. In general formula (40), X ⁵⁶ is preferably an alkylene chain having 1 to 4 carbon atoms or a cycloalkylene chain having 4 to 7 carbon atoms. The alkylene chain, cycloalkylene chain, alkyl group, and aryl group described above may be unsubstituted or substituted.

In general formulas (41) to (43), X ⁵⁷ to X ⁶¹ each independently represent an aliphatic structure having 1 to 6 carbon atoms, and X ⁶² and X ⁶³ each independently represent 1 carbon atom. represents an alkylene chain of ∼6 or a cycloalkylene chain of 4 to 10 carbon atoms. R ⁹³ to R ⁹⁷ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ⁹⁸ to R ¹⁰⁴ are Each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ¹⁰⁵ is hydrogen or represents an alkyl group, R ¹⁰⁶ and R ¹⁰⁷ each independently represents a substituent represented by the general formula (39), R ¹⁰⁸ is hydrogen, a substituent represented by the general formula (39), or It represents a substituent represented by general formula (40). m, n, o, p, and q each independently represent an integer of 0 to 10, r and s each independently represent an integer of 0 to 3, t, u, v, w , and x each independently represents an integer of 0 to 4. The alkylene chains, cycloalkylene chains, alkyl groups, cycloalkyl groups, aryl groups, and aliphatic structures described above may have heteroatoms and may be unsubstituted or substituted.

Among the (A2-3) acid-modified epoxy resins used in the present invention, the (A2-3) acid-modified epoxy resin having a structural unit represented by the general formula (43) has a terminal represented by the general formula (44) It is preferable to have a substituent represented by and/or a substituent represented by general formula (45).

In general formula (44), R ¹⁰⁹ represents a substituent represented by general formula (39). In general formula (45), X ⁶⁴ represents an aliphatic structure having 1 to 6 carbon atoms. R ¹¹⁰ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R ¹¹¹ and R ¹¹² each independently represent halogen, carbon It represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R ¹¹³ represents a substituent represented by general formula (39). α represents an integer from 0 to 10; β and γ represent integers of 0-4. In general formula (45), X ⁶⁴ preferably has an aliphatic structure with 1 to 4 carbon atoms. R ¹¹⁰ is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ¹¹¹ and R ¹¹² are each independently halogen, carbon An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferable.

<Structural Unit Derived from Aromatic Carboxylic Acid and its Derivative>
The (A2-3) acid-modified epoxy resin used in the present invention preferably contains a structural unit derived from an aromatic carboxylic acid or a derivative thereof. When the acid-modified epoxy resin (A2-3) contains a structural unit derived from an aromatic carboxylic acid or a derivative thereof, the heat resistance of the aromatic group can improve the heat resistance of the cured film. Examples of aromatic carboxylic acids and derivatives thereof include tetracarboxylic acids having an aromatic group, tricarboxylic acids having an aromatic group, tricarboxylic acid anhydrides having an aromatic group, dicarboxylic acids having an aromatic group, and aromatic groups. One or more selected from dicarboxylic acid anhydrides are preferable.

In addition, when (D1) a pigment is contained as a (D) coloring agent described later, (A2-3) an acid-modified epoxy resin containing a structural unit derived from an aromatic carboxylic acid or a derivative thereof can The steric hindrance of the group group can improve the dispersion stability of the (D1) pigment. Further, when (D1) pigment is (D1-1) organic pigment, the aromatic group in (A2-3) acid-modified epoxy resin interacts with the aromatic group of (D1-1) organic pigment, (D1-1) It is possible to improve the dispersion stability of the organic pigment.

Aromatic carboxylic acids and derivatives thereof include compounds contained in the above-described aromatic tetracarboxylic acids and/or derivatives thereof, aromatic tricarboxylic acids and/or derivatives thereof, and aromatic dicarboxylic acids and/or derivatives thereof. .

(A2-3) In the acid-modified epoxy resin, the content ratio of structural units derived from aromatic carboxylic acids and/or derivatives thereof to all structural units derived from carboxylic acids and derivatives thereof is 10 to 100 mol%. Preferably, 20 to 100 mol % is more preferable, and 30 to 100 mol % is even more preferable. When the content ratio is 10 to 100 mol %, the heat resistance of the cured film can be improved.

<Acidic group derived from carboxylic acid and its derivative>
The (A2-3) acid-modified epoxy resin used in the present invention preferably contains a structural unit derived from a carboxylic acid and its derivative, and (A2-3) the acid-modified epoxy resin preferably has an acidic group. (A2-3) Since the acid-modified epoxy resin has an acidic group, it is possible to improve the pattern processability with an alkaline developer and the resolution after development.

As the acidic group, a group exhibiting an acidity of less than pH 6 is preferred. Examples of groups exhibiting acidity of less than pH 6 include a carboxy group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, or a hydroxyimide group. A carboxy group, a carboxylic anhydride group, or a phenolic hydroxyl group is preferred, and a carboxy group or a carboxylic anhydride group is more preferred, from the viewpoint of improving pattern processability with an alkaline developer and improving resolution after development.

(A2-3) The content ratio of structural units derived from various monomer components in the acid-modified epoxy resin is ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis, and ash content measurement can be combined.

<Specific examples of (A2-3) acid-modified epoxy resin>
The acid-modified epoxy resin (A2-3) used in the present invention includes, for example, "KAYARAD" (registered trademark) PCR-1222H, CCR-1171H, TCR-1348H, ZAR-1494H, ZFR-1401H, The same ZCR-1798H, the same ZXR-1807H, the same ZCR-6002H, or the same ZCR-8001H (all of which are manufactured by Nippon Kayaku Co., Ltd.), or "NK OLIGO" (registered trademark) EA-6340, EA-7140, Alternatively, the same EA-7340 (both of which are manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.

<(A2-3) Physical properties of acid-modified epoxy resin>
The Mw of the acid-modified epoxy resin (A2-3) used in the present invention is preferably 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more in terms of polystyrene measured by GPC. The resolution after development can be improved as Mw is in the range mentioned above. On the other hand, Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less. When the Mw is within the range described above, the leveling property during coating and the pattern workability with an alkaline developer can be improved.

<(A2-4) acrylic resin>
The (A2-4) acrylic resin used in the present invention is, for example, one or more selected from a copolymer component having an acidic group, a copolymer component derived from a (meth)acrylic acid ester, and other copolymer components. and an acrylic resin obtained by radical copolymerization of the copolymerization component.

Examples of the copolymerization component having an acidic group, the copolymerization component derived from (meth)acrylic acid ester, and other copolymerization components include compounds described in International Publication No. 2017/057281.

The (A2-4) acrylic resin used in the present invention preferably has an ethylenically unsaturated double bond group. By including the (A2-4) acrylic resin having an ethylenically unsaturated double bond group in the negative photosensitive resin composition, the sensitivity during exposure can be improved. In addition, since the three-dimensional crosslinked structure to be formed is mainly composed of an alicyclic structure or an aliphatic structure, the softening point of the resin is suppressed from increasing, and a pattern shape with a low taper can be obtained. The mechanical properties of the resulting cured film can be improved. Therefore, it is suitable when the cured film is used for applications requiring mechanical properties.

The (A2-4) acrylic resin used in the present invention is a structural unit represented by general formula (61) and/or It is preferable to contain a structural unit represented by.

In general formulas (61) and (62), Rd ¹ and Rd ² are each independently an alkyl group having 1 to 10 carbon atoms, a cyclo It represents an alkyl group or an aryl group having 6 to 15 carbon atoms. R ²⁰⁰ to R ²⁰⁵ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. X ⁹⁰ and X ⁹¹ each independently represent a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms.

In general formulas (61) and (62), Rd ¹ and Rd ² each independently represent an alkyl group having 1 to 6 carbon atoms, a cyclo An alkyl group or an aryl group having 6 to 10 carbon atoms is preferred. Moreover, R ²⁰⁰ to R ²⁰⁵ are each independently preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X ⁹⁰ and X ⁹¹ are each independently preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. The alkyl group, cycloalkyl group, aryl group, alkylene chain, cycloalkylene chain, and arylene chain described above may have heteroatoms and may be unsubstituted or substituted.

The acrylic resin (A2-4) used in the present invention is preferably an acrylic resin (A2-4) obtained by radical copolymerization of a copolymerization component having an acidic group or another copolymerization component. As another copolymerization component, a copolymerization component having an aromatic group or a copolymerization component having an alicyclic group is preferable.

<Structural Unit Derived from Copolymerization Component Having Acidic Group>
The acrylic resin (A2-4) used in the present invention preferably contains a structural unit derived from a copolymer component having an acidic group, and the acrylic resin (A2-4) preferably has an acidic group. (A2-4) Since the acrylic resin has an acidic group, it is possible to improve the pattern processability with an alkaline developer and the resolution after development.

As the acidic group, a group exhibiting an acidity of less than pH 6 is preferred. Examples of groups exhibiting acidity of less than pH 6 include a carboxy group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, or a hydroxyimide group. A carboxy group, a carboxylic anhydride group, or a phenolic hydroxyl group is preferred, and a carboxy group or a carboxylic anhydride group is more preferred, from the viewpoint of improving pattern processability with an alkaline developer and improving resolution after development.

As the (A2-4) acrylic resin used in the present invention, when the (A2-4) acrylic resin has a carboxy group, the (A2-4) acrylic resin having no epoxy group is preferable. (A2-4) If the acrylic resin has both a carboxy group and an epoxy group, the carboxy group and the epoxy group may react during storage of the negative photosensitive resin composition coating solution. Therefore, it causes deterioration in the storage stability of the coating liquid of the resin composition. As the (A2-4) acrylic resin having no epoxy group, a copolymer component having a carboxy group or a carboxylic acid anhydride group and another copolymer component having no epoxy group were radically copolymerized (A2 -4) Acrylic resin is preferred.

<Structural Unit Derived from Copolymerization Component Having Aromatic Group>
The (A2-4) acrylic resin used in the present invention preferably contains a structural unit derived from a copolymer component having an aromatic group. (A2-4) When the acrylic resin contains a structural unit derived from a copolymer component having an aromatic group, the heat resistance of the aromatic group can improve the heat resistance of the cured film.

Further, as the (D) colorant described later, in particular when (D1) pigment is contained, (A2-4) acrylic resin contains a structural unit derived from a copolymer component having an aromatic group, so that an aromatic The steric hindrance of the group can improve the dispersion stability of the (D1) pigment. Furthermore, when (D1) pigment is (D1-1) organic pigment, (A2-4) the aromatic group in acrylic resin interacts with the aromatic group of (D1-1) organic pigment, so (D1 -1) It is possible to improve the dispersion stability of the organic pigment.

(A2-4) The content ratio of the structural units derived from the copolymerization component having an aromatic group to the structural units derived from all the copolymerization components in the acrylic resin is preferably 10 mol% or more, more preferably 20 mol% or more. Preferably, 30 mol % or more is more preferable. When the content ratio is 10 mol % or more, the heat resistance of the cured film can be improved. On the other hand, the content ratio is preferably 80 mol % or less, more preferably 75 mol % or less, and even more preferably 70 mol % or less. When the content ratio is 80 mol % or less, the sensitivity during exposure can be improved.

<Structural Unit Derived from Copolymerization Component Having Alicyclic Group>
The (A2-4) acrylic resin used in the present invention preferably contains a structural unit derived from a copolymer component having an alicyclic group. (A2-4) By containing a structural unit derived from a copolymer component having an alicyclic group in the acrylic resin, the heat resistance and transparency of the alicyclic group improve the heat resistance and transparency of the cured film. can be made

(A2-4) The content ratio of the structural unit derived from the copolymerization component having an alicyclic group in the structural units derived from all the copolymerization components in the acrylic resin is preferably 5 mol% or more, and is preferably 10 mol% or more. More preferably, 15 mol % or more is even more preferable. When the content ratio is 5 mol % or more, the heat resistance and transparency of the cured film can be improved. On the other hand, the content ratio is preferably 90 mol % or less, more preferably 85 mol % or less, and even more preferably 75 mol % or less. When the content ratio is 90 mol % or less, the mechanical properties of the cured film can be improved.

The (A2-4) acrylic resin used in the present invention includes a resin obtained by radically copolymerizing a copolymer component having an acidic group or another copolymer component, and further comprising an ethylenically unsaturated double bond group. and a resin obtained by a ring-opening addition reaction of an unsaturated compound having an epoxy group. By subjecting an unsaturated compound having an ethylenically unsaturated double bond group and an epoxy group to a ring-opening addition reaction, an ethylenically unsaturated double bond group can be introduced into the side chain of the (A2-4) acrylic resin. .

(A2-4) The content ratio of structural units derived from various copolymer components in the acrylic resin is determined by ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis, and It can be obtained by combining ash measurement and the like.

<(A2-4) Physical properties of acrylic resin>
The Mw of the acrylic resin (A2-4) used in the present invention is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more in terms of polystyrene measured by GPC. The resolution after development can be improved as Mw is 1,000 or more. On the other hand, Mw is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. When the Mw is 100,000 or less, leveling properties during coating and pattern processability with an alkaline developer can be improved.

(A2-4) The acrylic resin can be synthesized by a known method. Examples thereof include a method of radically copolymerizing the copolymerizable components in the presence of a radical polymerization initiator under air or nitrogen. As a method for radical copolymerization, for example, after sufficiently nitrogen-substituting the inside of the reaction vessel under air or by bubbling or reduced pressure degassing, the copolymerization component and the radical polymerization initiator are added in the reaction solvent, and 60- A method of reacting at 110° C. for 30 to 500 minutes can be used. Moreover, a chain transfer agent such as a thiol compound and/or a polymerization inhibitor such as a phenol compound may be used as necessary.

In the negative photosensitive resin composition of the present invention, the content ratio of (A1) the first resin in the total 100% by mass of the (A1) first resin and (A2) the second resin is 25% by mass or more. is preferable, 50% by mass or more is more preferable, 60% by mass or more is still more preferable, 70% by mass or more is even more preferable, and 80% by mass or more is particularly preferable. When the content is 25% by mass or more, the heat resistance of the cured film and the reliability of the light-emitting device can be improved. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. On the other hand, the content ratio of (A1) the first resin is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, even more preferably 95% by mass or less, and 90% by mass or less. is particularly preferred. When the content is 99% by mass or less, sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, halftone characteristics can be improved.

When the content ratio of the first resin (A1) and the second resin (A2) in the negative photosensitive resin composition of the present invention is within the preferred range described above, the heat resistance of the cured film can be improved. In addition, a pattern shape with a low taper can be obtained. Therefore, the cured film obtained from the negative photosensitive resin composition of the present invention can be used as an insulating layer such as a pixel dividing layer of an organic EL display, a TFT flattening layer, or a TFT protective layer with high heat resistance and a low taper pattern. It is suitable for applications where shape is required. In particular, in applications where problems due to heat resistance and pattern shape are assumed, such as element defects or characteristic deterioration due to degassing due to thermal decomposition, and disconnection of electrode wiring due to highly tapered pattern shape, the negative of the present invention can be used. By using the cured film of the type photosensitive resin composition, it is possible to manufacture a highly reliable device free from the above-described problems. In addition, since the negative photosensitive resin composition of the present invention contains (D) a coloring agent, which will be described later, it is possible to prevent the electrode wiring from becoming visible or to reduce the reflection of external light, thereby improving the contrast in image display. .

<(B) Radically polymerizable compound>
The negative photosensitive resin composition of the present invention preferably further contains (B) a radically polymerizable compound. (B) Radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in its molecule. At the time of exposure, radical polymerization of the radically polymerizable compound (B) proceeds by radicals generated from the photopolymerization initiator (C1), which will be described later, and the exposed portion of the film of the resin composition becomes insoluble in an alkaline developer. , a negative pattern can be formed.

By including (B) the radically polymerizable compound, UV curing during exposure is accelerated, and the sensitivity during exposure can be improved. In addition, the crosslink density after thermosetting is improved, and the hardness of the cured film can be improved.

(B) As the radically polymerizable compound, a compound having a (meth)acrylic group, which facilitates radical polymerization, is preferable. Compounds having two or more (meth)acrylic groups in the molecule are more preferable from the viewpoint of improving the sensitivity during exposure and the hardness of the cured film. (B) The double bond equivalent of the radically polymerizable compound is preferably 80 to 800 g/mol from the viewpoint of improving the sensitivity during exposure and forming a low tapered pattern.

(B) Radically polymerizable compounds include, in addition to (B1) fluorene skeleton-containing radically polymerizable compound and (B2) indane skeleton-containing radically polymerizable compound, which will be described later, for example, diethylene glycol di(meth)acrylate, triethylene glycol di( meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylol Propane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate acrylates, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapenta Erythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)) Acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, or 1,3-bis((meth)acryloxyethyl)isocyanuric acid, or acids thereof Variants are included. From the viewpoint of improving the resolution after development, compounds obtained by ring-opening addition reaction of a compound having two or more glycidoxy groups in the molecule and an unsaturated carboxylic acid having an ethylenically unsaturated double bond group. , polybasic carboxylic acids or polybasic carboxylic acid anhydrides are also preferred.

The content of the (B) radically polymerizable compound in the negative photosensitive resin composition of the present invention is 15 when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. It is preferably at least 20 parts by mass, more preferably at least 25 parts by mass, and particularly preferably at least 30 parts by mass. When the content is 15 parts by mass or more, the sensitivity at the time of exposure can be improved, and a cured film having a pattern shape with a low taper can be obtained. On the other hand, the content of (B) the radically polymerizable compound is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content is 65 parts by mass or less, the heat resistance of the cured film can be improved, and a low taper pattern shape can be obtained.

<(B1) Fluorene Skeleton-Containing Radically Polymerizable Compound and (B2) Indane Skeleton-Containing Radically Polymerizable Compound>
In the negative photosensitive resin composition of the present invention, the (B) radically polymerizable compound is further selected from the group consisting of (B1) a fluorene skeleton-containing radically polymerizable compound and (B2) an indane skeleton-containing radically polymerizable compound. It is preferable to contain one or more types.

(B1) The fluorene skeleton-containing radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups and a fluorene skeleton in the molecule. (B2) Indane skeleton-containing radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups and an indane skeleton in the molecule.

By including (B1) a fluorene skeleton-containing radically polymerizable compound or (B2) an indane skeleton-containing radically polymerizable compound, it is possible to improve the sensitivity during exposure and control the pattern shape after development, and to reduce the taper after heat curing. Shape patterning is possible. In addition, it is possible to form a forward tapered pattern by pattern shape control after development, so that halftone characteristics can be improved. Moreover, it is possible to suppress a change in the width of the pattern opening before and after thermal curing.

Furthermore, when (D1a-1a) a benzofuranone-based black pigment is used as the (Da) black agent, which will be described later, a development residue derived from the pigment may occur due to the insufficient alkali resistance of the pigment described above. In such a case, by including (B3) a flexible chain-containing aliphatic radically polymerizable compound and (B1) a fluorene skeleton-containing radically polymerizable compound or (B2) an indane skeleton-containing radically polymerizable compound, which will be described later, the above-mentioned It is possible to suppress the generation of development residues derived from pigments.

As the (B1) fluorene skeleton-containing radically polymerizable compound and (B2) the indane skeleton-containing radically polymerizable compound, a compound having a (meth)acrylic group, which facilitates the progress of radical polymerization, is preferable. Compounds having two or more (meth)acrylic groups in the molecule are more preferable from the viewpoint of improving sensitivity during exposure and suppressing residue after development.

Examples of the (B1) fluorene skeleton-containing radically polymerizable compound include 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth) ) acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene, 9,9-bis[4-(2-hydroxy-3-(meth)acryloxypropoxy)phenyl] Fluorene, or 9,9-bis[3,4-bis(2-(meth)acryloxyethoxy)phenyl]fluorene, or OGSOL (registered trademark) EA-50P, EA-0200, EA-0250P, EA -0300, EA-500, EA-1000, EA-F5510, or GA-5000 (all of which are manufactured by Osaka Gas Chemicals Co., Ltd.).

(B2) The indane skeleton-containing radically polymerizable compound includes, for example, 1,1-bis[4-(2-(meth)acryloxyethoxy)phenyl]indane, 1,1-bis(4-(meth)acryloxy phenyl)indane, 1,1-bis[4-(2-hydroxy-3-(meth)acryloxypropoxy)phenyl]indane, 1,1-bis[3,4-bis(2-(meth)acryloxyethoxy) )phenyl]indane, 2,2-bis[4-(2-(meth)acryloxyethoxy)phenyl]indane, or 2,2-bis(4-(meth)acryloxyphenyl)indane.

(B1) fluorene skeleton-containing radically polymerizable compound and (B2) indane skeleton-containing radically polymerizable compound can be synthesized by a known method. For example, the synthesis method described in International Publication No. 2008/139924 can be mentioned.

The total content of (B1) a fluorene skeleton-containing radically polymerizable compound and (B2) an indane skeleton-containing radically polymerizable compound in the negative photosensitive resin composition of the present invention is (A) an alkali-soluble resin and (B) When the total of the radically polymerizable compounds is 100 parts by mass, it is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more. Part by mass or more is particularly preferred. When the content is 0.5 parts by mass or more, the sensitivity at the time of exposure can be improved, and a low tapered pattern can be formed after thermal curing. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. On the other hand, the total content of (B1) the fluorene skeleton-containing radically polymerizable compound and (B2) the indane skeleton-containing radically polymerizable compound is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less. More preferably, 18 parts by mass or less is even more preferable, and 15 parts by mass or less is particularly preferable. When the content is 25 parts by mass or less, it is possible to suppress the change in pattern opening dimension width before and after heat curing, and to suppress the generation of residues after development.

<(B3) Flexible Chain-Containing Aliphatic Radically Polymerizable Compound>
The negative photosensitive resin composition of the present invention preferably further contains (B3) a flexible chain-containing aliphatic radically polymerizable compound as (B) a radically polymerizable compound. (B3) A flexible chain-containing aliphatic radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups and a flexible skeleton such as an aliphatic chain or an oxyalkylene chain in the molecule.

By including (B3) the flexible chain-containing aliphatic radically polymerizable compound, UV curing during exposure proceeds efficiently, and the sensitivity during exposure can be improved. In addition, when the (D1) pigment is contained as the (D) colorant described later, the (D1) pigment is fixed to the cured portion by crosslinking of the (B3) flexible chain-containing aliphatic radically polymerizable compound during UV curing. (D1), it is possible to suppress the generation of post-development residue derived from the pigment. Moreover, it is possible to suppress a change in the width of the pattern opening before and after thermal curing.

Furthermore, when (D1a-1a) benzofuranone-based black pigment is contained as (Da) black agent, which will be described later, in particular, as described above, pigment-derived development residue may occur due to insufficient alkali resistance of this pigment. be. Even in such a case, the inclusion of (B3) the flexible chain-containing aliphatic radically polymerizable compound can suppress the development residue derived from the above pigment.

(B3) Flexible chain-containing aliphatic radically polymerizable compound is preferably a compound having a group represented by general formula (24) and three or more groups represented by general formula (25) in the molecule.

In general formula (24), R ¹²⁵ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. Z ¹⁷ represents a group represented by general formula (29) or a group represented by general formula (30). a represents an integer of 1 to 10, b represents an integer of 1 to 4, c represents 0 or 1, d represents an integer of 1 to 4, e represents 0 or 1 . If c is 0, then d is 1. In general formula (25), R ¹²⁶ to R ¹²⁸ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. In general formula (30), R ¹²⁹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. In general formula (24), c is preferably 1, and e is preferably 1. In general formula (25), R ¹²⁶ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a methyl group. R ¹²⁷ and R ¹²⁸ are each independently preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen. In general formula (30), R ¹²⁹ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a methyl group. In general formula (24), when c is 1, it is possible to suppress the generation of residues after development.

(B3) Flexible chain-containing aliphatic radical polymerizable compound preferably has at least one lactone-modified chain and/or at least one lactam-modified chain. (B3) The flexible chain-containing aliphatic radically polymerizable compound has at least one lactone-modified chain and/or at least one lactam-modified chain, so that generation of residue after development can be suppressed. In the general formula (24) described above, when c is 1 and e is 1, (B3) the flexible chain-containing aliphatic radically polymerizable compound has at least one lactone-modified chain and/or at least one It has two lactam-modified chains.

(B3) The number of ethylenically unsaturated double bond groups in the molecule of the flexible chain-containing aliphatic radically polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. When the number of ethylenically unsaturated double bond groups is 2 or more, sensitivity during exposure can be improved. On the other hand, the number of ethylenically unsaturated double bond groups in the molecule of (B3) the flexible chain-containing aliphatic radically polymerizable compound is preferably 12 or less, more preferably 10 or less, even more preferably 8 or less, and 6 1 or less is particularly preferred. When the number of ethylenically unsaturated double bond groups is 12 or less, a pattern with a low taper shape can be formed after heat curing, and a change in pattern opening dimension width before and after heat curing can be suppressed.

(B3) Flexible chain-containing aliphatic radically polymerizable compounds include compounds having 3 or more ethylenically unsaturated double bond groups in the molecule, such as ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated Dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, δ-valerolactone-modified dipentaerythritol hexa(meth)acrylate, γ-butyrolactone-modified dipentaerythritol hexa(meth)acrylate, β - Propiolactone-modified dipentaerythritol hexa (meth) acrylate, ε-caprolactam-modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified dipentaerythritol penta (meth) acrylate, ε-caprolactone-modified trimethylolpropane tri(meth) ) acrylate, ε-caprolactone-modified ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-modified glycerin tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate , or ε-caprolactone-modified 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, “KAYARAD” (registered trademark) DPEA-12, DPCA-20, DPCA-30, DPCA-60, Or the same DPCA-120 (all of them are manufactured by Nippon Kayaku Co., Ltd.), or "NK ESTER" (registered trademark) A-DPH-6E, A-DPH-6P, M-DPH-6E, A-9300 -1CL or A-9300-3CL (both of which are manufactured by Shin-Nakamura Chemical Co., Ltd.).

Compounds having two ethylenically unsaturated double bond groups in the molecule include, for example, ε-caprolactone-modified neopentyl hydroxypivalate di(meth)acrylate, ε-caprolactone-modified trimethylolpropane di(meth)acrylate, ε-caprolactone-modified ditrimethylolpropane di(meth)acrylate, ε-caprolactone-modified glycerin di(meth)acrylate, ε-caprolactone-modified pentaerythritol di(meth)acrylate, ε-caprolactone-modified dimethylol-tricyclodecane di(meth)acrylate , ε-caprolactone-modified 1,3-bis((meth)acryloxyethyl)isocyanuric acid, or ε-caprolactone-modified 1,3-bis((meth)acryloxyethyl)isocyanuric acid, or “KAYARAD” (registered trademark) HX-220 or HX-620 (both of which are manufactured by Nippon Kayaku Co., Ltd.).

(B3) Flexible chain-containing aliphatic radically polymerizable compound can be synthesized by a known method.

The content of the (B3) flexible chain-containing aliphatic radically polymerizable compound in the negative photosensitive resin composition of the present invention is 100 parts by mass for the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound. WHEREIN: 5 mass parts or more are preferable, 10 mass parts or more are more preferable, 15 mass parts or more are still more preferable, and 20 mass parts or more are especially preferable. When the content is 5 parts by mass or more, the sensitivity during exposure can be improved, and the generation of residue after development can be suppressed. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing. On the other hand, the content of (B3) the flexible chain-containing aliphatic radically polymerizable compound is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less. When the content is 45 parts by mass or less, a cured film having a low taper pattern can be obtained.

<(B4) Alicyclic Group-Containing Radically Polymerizable Compound>
The negative photosensitive resin composition of the present invention preferably further contains (B4) an alicyclic group-containing radically polymerizable compound as (B) a radically polymerizable compound. (B4) Alicyclic group-containing radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups and an alicyclic group in the molecule.

By including (B4) an alicyclic group-containing radically polymerizable compound, it is possible to suppress a change in pattern opening dimension width before and after heat curing. This is presumably because alicyclic groups were introduced into the film by UV curing during exposure, thereby improving the heat resistance and suppressing reflow at the bottom of the pattern. In addition to the above, it is possible to form a forward tapered pattern by pattern shape control after development, and to form a low tapered pattern after heat curing. It is speculated that this is because the hydrophobicity of the alicyclic group inhibits the penetration of the alkaline developer into the film during development, and the steric hindrance of the alicyclic group inhibits excessive curing during heat curing. be done.

The negative photosensitive resin composition of the present invention preferably contains (B4) an alicyclic group-containing radically polymerizable compound and (F) a polyfunctional thiol compound described later. By using (B4) an alicyclic group-containing radical polymerizable compound and (F) a polyfunctional thiol compound in combination, it is possible to suppress changes in the pattern opening dimension width before and after heat curing, and to have a low tapered shape after development. pattern can be formed. This is probably because (F) polyfunctional thiol compound suppresses oxygen inhibition on the film surface, thereby promoting UV curing of (B4) alicyclic group-containing radically polymerizable compound during exposure. That is, it is presumed that UV curing at the time of exposure improved the heat resistance and hydrophobicity derived from the alicyclic group. (B4) Alicyclic group-containing radically polymerizable compound is likely to inhibit UV curing due to oxygen inhibition on the film surface and steric hindrance of the alicyclic group. This is thought to be due to the marked promotion of

(B4) The number of ethylenically unsaturated double bond groups in the molecule of the alicyclic group-containing radically polymerizable compound is more preferably 2 or more, and even more preferably 3 or more. When the number of ethylenically unsaturated double bond groups is 2 or more, sensitivity during exposure can be improved. On the other hand, the number of ethylenically unsaturated double bond groups in the molecule of (B4) the alicyclic group-containing radically polymerizable compound is preferably 10 or less, more preferably 6 or less. When the number of ethylenically unsaturated double bond groups is 10 or less, a low tapered pattern can be formed after heat curing.

As the alicyclic group which the alicyclic group-containing radically polymerizable compound (B4) has in the molecule, a condensed polycyclic alicyclic skeleton is preferable. By having a condensed polycyclic alicyclic skeleton, it is possible to suppress a change in pattern opening dimension width before and after heat curing. In addition, it is possible to form a forward tapered pattern by pattern shape control after development, and to form a low tapered pattern after thermal curing.
Examples of condensed polycyclic alicyclic skeletons include bicyclo[4.3.0]nonane skeleton, bicyclo[5.4.0]undecane skeleton, bicyclo[2.2.2]octane skeleton, tricyclo[5.2 .1.0 ^2,6 ]decane skeleton, pentacyclopentadecane skeleton, adamantane skeleton or hydroxyadamantane skeleton.

(B4) Alicyclic group-containing radically polymerizable compound, for example, dimethylol-bicyclo[4.3.0]nonane di(meth)acrylate, dimethylol-bicyclo[5.4.0]undecane di(meth)acrylate, dimethylol -bicyclo[2.2.2]octane di(meth)acrylate, dimethylol-tricyclo[5.2.1.0 ^2,6 ]decane di(meth)acrylate, dimethylol-pentacyclopentadecane di(meth)acrylate, 1, 3-adamantane di(meth)acrylate, 1,3,5-adamantane tri(meth)acrylate or 5-hydroxy-1,3-adamantane di(meth)acrylate.

(B4) The alicyclic group-containing radically polymerizable compound can be synthesized by a known method.

The content of the (B4) alicyclic group-containing radically polymerizable compound in the negative photosensitive resin composition of the present invention is 100 parts by mass for the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound. 1 part by mass or more is preferred, 2 parts by mass or more is more preferred, 3 parts by mass or more is even more preferred, 5 parts by mass or more is even more preferred, and 10 parts by mass or more is particularly preferred. When the content is 1 part by mass or more, it is possible to suppress the change in the width of the pattern opening before and after the heat curing. In addition, it is possible to form a forward tapered pattern by pattern shape control after development, and to form a low tapered pattern after heat curing. On the other hand, the content of (B4) the alicyclic group-containing radically polymerizable compound is preferably 30 parts by mass or less, more preferably 27 parts by mass or less, even more preferably 25 parts by mass or less, and even more preferably 22 parts by mass or less. , and 20 parts by mass or less are particularly preferred. When the content is 30 parts by mass or less, it is possible to suppress the change in the width of pattern openings before and after heat curing, and to suppress the generation of residues after development.

<(C1) Photoinitiator>
The negative photosensitive resin composition of the present invention further contains (C1) a photopolymerization initiator as (C) a photosensitive agent. (C1) Photopolymerization initiator refers to a compound that cleaves bonds and/or reacts with exposure to generate radicals. By containing the photopolymerization initiator (C1), the radical polymerization of the radically polymerizable compound (B) described above proceeds, and the exposed portion of the film of the resin composition becomes insoluble in an alkaline developer, thereby producing a negative film. A pattern of molds can be formed. In addition, UV curing during exposure is accelerated, and sensitivity can be improved.

In addition, by including a specific amount or more of the photopolymerization initiator (C1), it is possible to suppress a change in the width of the pattern opening before and after heat curing. This is thought to be due to an increase in the amount of radicals generated from the photopolymerization initiator (C1) during exposure. That is, by increasing the amount of radicals generated during exposure, the probability of collision between the generated radicals and the ethylenically unsaturated double bond groups in the above-mentioned (B) radically polymerizable compound increases, and UV curing is promoted. It is presumed that the improvement in the crosslink density suppresses the reflow of the tapered portion of the pattern and the bottom of the pattern during heat curing, thereby suppressing the change in the width of the pattern opening before and after heat curing.

(C1) Photopolymerization initiators include, for example, benzyl ketal-based photopolymerization initiators, α-hydroxyketone-based photopolymerization initiators, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and biimidazole. photopolymerization initiator, oxime ester photopolymerization initiator, acridine photopolymerization initiator, titanocene photopolymerization initiator, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, aromatic ketoester photopolymerization initiator , or a benzoic acid ester-based photopolymerization initiator is preferable, and from the viewpoint of improving sensitivity during exposure, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, Biimidazole-based photopolymerization initiators, oxime ester-based photopolymerization initiators, acridine-based photopolymerization initiators, or benzophenone-based photopolymerization initiators are more preferred, α-aminoketone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. , biimidazole-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are more preferred.

Benzyl ketal photopolymerization initiators include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one.

Examples of α-hydroxyketone-based photopolymerization initiators include 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1 -one, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, or 2-hydroxy-1-[4-[4- (2-Hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one.

Examples of α-aminoketone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, or 3,6-bis(2-methyl -2-morpholinopropionyl)-9-octyl-9H-carbazole.

Acylphosphine oxide-based photopolymerization initiators include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxy benzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

Examples of biimidazole-based photopolymerization initiators include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′, 5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-biimidazole, 2,2',5-tris(2-fluorophenyl) -4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-biimidazole or 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

Examples of oxime ester photopolymerization initiators include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxy carbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-( O-benzoyl)oxime, 1-[4-[4-carboxyphenylthio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[4-[4-(2-hydroxyethoxy ) phenylthio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl ) oxime, 1-[4-(phenylthio)phenyl]-2-cyclopentylethane-1,2-dione-2-(O-acetyl)oxime, 1-[9,9-diethylfluoren-2-yl]propane- 1,2-dione-2-(O-acetyl)oxime, 1-[9,9-di-n-propyl-7-(2-methylbenzoyl)-fluoren-2-yl]ethanone-1-(O- Acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2 -methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-1-(O-acetyl)oxime, or 1-(9-ethyl -6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

Examples of acridine photopolymerization initiators include 1,7-bis(acridin-9-yl)-n-heptane.

Titanocene-based photopolymerization initiators include, for example, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (IV), or bis(η ⁵ -3-methyl-2,4-cyclopentadien-1-yl)-bis(2,6-difluorophenyl)titanium (IV).

Examples of benzophenone-based photopolymerization initiators include benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4- Hydroxybenzophenone, alkylated benzophenone, 3,3′,4,4′-tetrakis(t-butylperoxycarbonyl)benzophenone, 4-methylbenzophenone, dibenzylketone, or fluorenone.

Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone.

Examples of aromatic ketoester-based photopolymerization initiators include methyl 2-phenyl-2-oxyacetate.

Examples of benzoic acid ester-based photopolymerization initiators include ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. be done.

The content of the photopolymerization initiator (C1) in the negative photosensitive resin composition of the present invention is 0 when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. 0.1 parts by mass or more is preferred, 0.5 parts by mass or more is more preferred, 0.7 parts by mass or more is even more preferred, and 1 part by mass or more is particularly preferred. When the content is 0.1 parts by mass or more, the sensitivity during exposure can be improved. In addition, the content of the photopolymerization initiator (C1) is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, still more preferably 14 parts by mass or more, from the viewpoint of controlling the pattern opening dimension width, and 15 parts by mass. The above are particularly preferred. When the content is 10 parts by mass or more, it is possible to suppress the change in the width of the pattern opening before and after heat curing. On the other hand, the content of the photopolymerization initiator (C1) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 22 parts by mass or less, and particularly preferably 20 parts by mass or less. When the content is 30 parts by mass or less, the resolution after development can be improved, and a cured film with a low tapered pattern can be obtained.

<(C1-1) Specific oxime ester photopolymerization initiator>
The negative photosensitive resin composition of the present invention has (C1) a photopolymerization initiator having one or more structures selected from the group consisting of (I), (II), and (III) (C1-1 ) contains an oxime ester photopolymerization initiator (hereinafter referred to as “(C1-1) specific oxime ester photopolymerization initiator”).

(I) one or more structures selected from the group consisting of a naphthalenecarbonyl structure, a trimethylbenzoyl structure, a thiophenecarbonyl structure, and a furancarbonyl structure (II) a nitro group, a carbazole structure, and a group represented by general formula (11) (III) a nitro group and one or more structures selected from the group consisting of a fluorene structure, a dibenzofuran structure, a dibenzothiophene structure, a naphthalene structure, a diphenylmethane structure, a diphenylamine structure, a diphenylether structure, and a diphenylsulfide structure;

In general formula (11), X ⁷ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. When X ⁷ is a direct bond, a C 1-10 alkylene group, or a C 4-10 cycloalkylene group, R ²⁹ is hydrogen, a C 1-10 alkyl group, a C 4-10 represents a cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group; When X ⁷ is an arylene group having 6 to 15 carbon atoms, R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carbon haloalkyl group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 10 carbon atoms, heterocyclic group having 4 to 10 carbon atoms, heterocyclic oxy group having 4 to 10 carbon atoms, acyl group having 2 to 10 carbon atoms, or nitro represents a group. R ³⁰ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a represents 0 or 1, and b represents an integer of 0-10.

In general formula (11), X ⁷ is preferably an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving solubility in solvents, or an arylene group having 6 to 15 carbon atoms from the viewpoint of improving sensitivity during exposure. preferable. R ²⁹ is preferably a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving solubility in solvents. R ²⁹ is a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or a A heterocyclic group, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group is preferred. R ³⁰ is preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl, from the viewpoint of improving sensitivity during exposure. From the viewpoint of improving sensitivity during exposure, a is preferably 0.

The group represented by the general formula (11) is a group having an oxime ester structure, and is a group having a structure that generates radicals by bond cleavage and/or reaction with UV light during exposure. Note that the fluorene structure, carbazole structure, dibenzofuran structure, dibenzothiophene structure, naphthalene structure, diphenylmethane structure, diphenylamine structure, diphenyl ether structure, or diphenyl sulfide structure in (II) or (III) described above is the oxime ester structure described above. represents the base skeleton to which the group having In addition, the naphthalenecarbonyl structure, trimethylbenzoyl structure, thiophenecarbonyl structure, furancarbonyl structure, and nitro group in (I), (II), or (III) above are bonded to groups having the above-described oxime ester structure. represents a structure or a group that binds to the base skeleton.

(C1-1) The specific oxime ester photopolymerization initiator increases the absorbance in the ultraviolet region in the molecule, radical cures deep in the film during exposure, and radical cure due to an increase in the amount of radicals generated during exposure. An oxime ester compound having a specific conjugated structure that can promote

(C1-1) By including a specific oxime ester photopolymerization initiator, sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, halftone characteristics can be improved. It is presumed that this is because radical curing in the deep part of the film became possible at the time of exposure. In addition, (C1-1) the specific conjugated structure of the specific oxime ester photopolymerization initiator interacts with the aromatic groups of the (A1) first resin and (A2) the second resin. The entire film is compatibilized at the time of exposure, and the increase in the amount of radicals generated during exposure promotes radical hardening deep into the film. This is thought to be because it is possible to suppress

In addition, (C1-1) containing a specific oxime ester photopolymerization initiator can suppress a change in the width of the pattern opening before and after heat curing. As mentioned above, this suppresses side etching caused by the developer during alkaline development, making it possible to form a pattern with a low taper shape after development. It is presumed that this is because the film has a high molecular weight, and reflow at the pattern bottom during heat curing is suppressed.

From the viewpoint of improving sensitivity during exposure, reducing taper by controlling pattern shape after development, suppressing changes in pattern opening width before and after heat curing, and improving halftone characteristics, (C1-1) specific oxime ester photopolymerization The initiator contains one or more selected from the group consisting of the compound represented by the general formula (12), the compound represented by the general formula (13), and the compound represented by the general formula (14). is preferred, and a compound represented by general formula (13) is more preferred.

In general formulas (12) to (14), X ¹ to X ⁶ are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or 6 to 6 carbon atoms. represents 15 arylene groups. Y ¹ to Y ³ each independently represent carbon, nitrogen, oxygen, or sulfur. R ³¹ to R ³⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or It represents a hydroxyalkyl group having 1 to 10 carbon atoms. R ³⁷ to R ³⁹ each independently represent a group represented by general formula (15), a group represented by general formula (16), a group represented by general formula (17), or general formula (18) represents a group represented by or a nitro group. R ⁴⁰ to R ⁴⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or represents a group forming a ring; R ⁴⁶ to R ⁴⁸ each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms. , an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. R ⁴⁹ to R ⁵¹ each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or represents a nitro group. R ⁵² to R ⁵⁴ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a represents an integer of 0 to 3, b represents 0 or 1, c represents an integer of 0 to 5, d represents 0 or 1, e represents an integer of 0 to 4 , f represents an integer of 0 to 2; g, h, and i each independently represent an integer of 0 to 2; j, k, and l each independently represent 0 or 1; and m, n, and o each independently represent an integer of 0 to 10. However, when Y ¹ is nitrogen, R ³⁷ is a nitro group, and X ⁴ is an arylene group having 6 to 15 carbon atoms, R ⁴⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms. aryl group having 6 to 15 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 10 carbon atoms, heterocyclic group having 4 to 10 carbon atoms, heterocyclic oxy group having 4 to 10 carbon atoms , represents an acyl group having 2 to 10 carbon atoms, or a nitro group.

In general formulas (12) to (14), X ¹ to X ⁶ are each independently preferably an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving solubility in solvents, and improving sensitivity during exposure. From the point of view, an arylene group having 6 to 15 carbon atoms is preferable. Examples of the ring having 4 to 10 carbon atoms formed by R ⁴⁰ to R ⁴⁵ include a benzene ring and a cyclohexane ring. R ⁴⁶ to R ⁴⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a A haloalkoxy group having 1 to 10 carbon atoms is preferred, and a fluoroalkyl group having 1 to 10 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms is more preferred. R ⁴⁶ to R ⁴⁸ each independently represent a haloalkyl group having 1 to 10 carbon atoms and a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving sensitivity during exposure and forming a low tapered pattern after development. or an acyl group having 2 to 10 carbon atoms, more preferably a fluoroalkyl group having 1 to 10 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms. R ⁴⁹ to R ⁵¹ are each independently a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving solubility in solvents. is preferred, and a fluoroalkyl group having 1 to 10 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms is more preferred. R ⁴⁹ to R ⁵¹ each independently represent a haloalkyl group having 1 to 10 carbon atoms and a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving sensitivity during exposure and forming a low tapered pattern after development. group, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group, a fluoroalkyl group having 1 to 10 carbon atoms, or a carbon A fluoroalkoxy group of numbers 1 to 10 is more preferred. From the viewpoint of improving sensitivity during exposure, R ⁵² to R ⁵⁴ are each independently preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, and methyl. More preferred. j, k, and l are each independently preferably 0 from the viewpoint of improving sensitivity during exposure.

In addition, from the viewpoint of improving the sensitivity during exposure, reducing the taper by controlling the pattern shape after development, suppressing changes in the width of the pattern opening before and after heat curing, and improving the halftone characteristics, (C1-1) a specific oxime ester The photopolymerization initiator preferably contains a compound represented by general formula (12) and/or a compound represented by general formula (13). In general formulas (12) and (13), Y ¹ and Y ² are preferably carbon or nitrogen. R ⁴⁶ and R ⁴⁷ preferably contain at least an alkenyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 1 to 6 carbon atoms. R ⁴⁹ and R ⁵⁰ preferably contain at least an alkenyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 1 to 6 carbon atoms. This is probably because the inclusion of alkenyl groups makes it possible to further increase the compatibility between the resin and the initiator, and UV curing during exposure proceeds efficiently even in deep portions of the film.

Examples of alkenyl groups include vinyl group, 1-methylethenyl group, allyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, 3-butenyl group, or cinnamyl group .

In general formulas (15) to (18), R ⁵⁵ to R ⁵⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. , an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or a group forming a ring. Examples of the ring formed by a plurality of R ⁵⁵ to R ⁵⁸ include benzene ring, naphthalene ring, anthracene ring, cyclopentane ring and cyclohexane ring. a is an integer of 0-7, b is an integer of 0-2, and c and d are each independently an integer of 0-3. A benzene ring or a naphthalene ring is preferable as the ring formed by a plurality of R ⁵⁵ to R ⁵⁸ .

(C1-1) The specific oxime ester photopolymerization initiator preferably has a halogen-substituted group. (C1-1) When the specific oxime ester-based photopolymerization initiator has a halogen-substituted group, the solubility in a solvent is improved. In addition, the compatibility with (A1) the first resin and (A2) the second resin is improved, the sensitivity at the time of exposure can be improved, and a low tapered pattern can be formed after development. can. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. Fluorine is preferred as the halogen. This is the case where (C1-1) a specific oxime ester photopolymerization initiator has a group substituted with fluorine, as the above-mentioned (A1) first resin, (A1-1) polyimide, (A1- 2) At least one type selected from polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor contains a structural unit having a fluorine atom, so that the resin and the initiator This is thought to be because the compatibility of the film can be further enhanced, and UV curing at the time of exposure proceeds efficiently even in the deep part of the film.

Groups substituted with halogen include, for example, fluoromethyl group, fluoroethyl group, chloroethyl group, bromoethyl group, iodoethyl group, trifluoromethyl group, trifluoropropyl group, trichloropropyl group, tetrafluoropropyl group, trifluoropentyl group , tetrafluoropentyl group, pentafluoropentyl group, heptafluoropentyl group, heptafluorodecyl group, fluorocyclopentyl group, tetrafluorocyclopentyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethoxy group, trifluoropropoxy group, tetra A fluoropropoxy group, a trifluoropentyloxy group, a pentafluoropentyloxy group, a tetrafluorocyclopentyloxy group, or a pentafluorophenoxy group can be mentioned.

(C1-1) Specific oxime ester photopolymerization initiators include, for example, compounds having the structures shown below (OXL-1 to OXL-102).

(C1-1) A specific oxime ester photopolymerization initiator can be synthesized by a known method. Examples thereof include the synthesis methods described in JP-A-2013-190459, JP-A-2016-191905, and International Publication No. 2014/500852.

(C1-1) The maximum absorption wavelength of the specific oxime ester photopolymerization initiator is preferably 330 nm or longer, more preferably 340 nm or longer, and even more preferably 350 nm or longer. When the maximum absorption wavelength is 330 nm or more, the sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. On the other hand, (C1-1) the maximum absorption wavelength of the specific oxime ester photopolymerization initiator is preferably 410 nm or less, more preferably 400 nm or less, still more preferably 390 nm or less, and particularly preferably 380 nm or less. When the maximum absorption wavelength is 410 nm or less, the sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics.

In addition, when the maximum transmission wavelength of (Da) the black agent described later is 330 to 410 nm, (C1-1) the maximum absorption wavelength of the specific oxime ester photopolymerization initiator is 330 to 410 nm. Sensitivity can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. It is believed that this is because the UV light during exposure can reach deep into the film, and UV curing proceeds efficiently even in the deep part of the film.

The maximum absorption wavelength and maximum transmission wavelength refer to the wavelengths showing maximum absorption and maximum transmission in the absorption spectrum and transmission spectrum within the wavelength range of 300 to 800 nm.

(C1-1) Absorbance at a wavelength of 360 nm in a 0.01 g/L propylene glycol monomethyl ether acetate solution of a specific oxime ester photopolymerization initiator is preferably 0.20 or more, more preferably 0.25 or more, 0.30 or more is more preferred, 0.35 or more is even more preferred, 0.40 or more is particularly preferred, and 0.45 or more is most preferred. When the absorbance is 0.20 or more, the sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. On the other hand, (C1-1) in a 0.01 g/L propylene glycol monomethyl ether acetate solution of the specific oxime ester photopolymerization initiator, the absorbance at a wavelength of 360 nm is preferably 1.00 or less. When the absorbance is 1.00 or less, the generation of residue after development can be suppressed, and the resolution after development can be improved.

The content of the specific oxime ester photopolymerization initiator (C1-1) in the negative photosensitive resin composition of the present invention is the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound, which is 100 mass. When expressed as parts, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more. When the content is 0.5 parts by mass or more, the sensitivity during exposure can be improved. In addition, the content of (C1-1) the specific oxime ester photopolymerization initiator is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, from the viewpoint of pattern shape control after development and after heat curing. 5 parts by mass or more is more preferable, and 7 parts by mass or more is particularly preferable. When the content is 3 parts by mass or more, a pattern with a low taper shape can be formed after development, and a change in pattern opening width before and after heat curing can be suppressed. In addition, halftone characteristics can be improved. On the other hand, the content of the specific oxime ester photopolymerization initiator (C1-1) is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, even more preferably 20 parts by mass or less, and particularly 15 parts by mass or less. preferable. When the content is 25 parts by mass or less, the resolution after development can be improved, and a cured film with a low tapered pattern can be obtained. In addition, the content of the specific oxime ester photopolymerization initiator (C1-1) is preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and 15 parts by mass or less from the viewpoint of pattern shape control after development. is more preferable, and 13 parts by mass or less is particularly preferable. When the content is 20 parts by mass or less, it is possible to form a pattern with a low taper shape after development, and to suppress a change in pattern opening dimension width before and after heat curing.

<(C1-2) α-Aminoketone Photopolymerization Initiator, (C1-3) Acylphosphine Oxide Photopolymerization Initiator and (C1-4) Biimidazole Photopolymerization Initiator>
The negative photosensitive resin composition of the present invention further comprises (C1) a photopolymerization initiator such as (C1-2) an α-aminoketone photopolymerization initiator and (C1-3) an acylphosphine oxide photopolymerization initiator. and (C1-4) a biimidazole-based photopolymerization initiator.

(C1-2) α-aminoketone-based photopolymerization initiator, (C1-3) acylphosphine oxide-based photopolymerization initiator and (C1-4) one or more selected from the group consisting of biimidazole-based photopolymerization initiator By containing it, the sensitivity at the time of exposure can be improved. These photopolymerization initiators have absorption wavelengths in a wavelength region different from the absorption wavelength of the specific oxime ester photopolymerization initiator (C1-1) described above, so UV light during exposure can be more efficiently radicalized. This is probably because it can be used for curing. In addition to the above, it is possible to suppress the change in the width of the pattern opening before and after heat curing. This is presumed to be due to the following reasons, in addition to the fact that radical curing progressed more efficiently due to the difference in absorption wavelength. (C1-2) α-aminoketone-based photopolymerization initiator, (C1-3) acylphosphine oxide-based photopolymerization initiator and (C1-4) biimidazole-based photopolymerization initiator contain nitrogen or phosphorus in the molecule Therefore, it is considered that amine or phosphine is generated by photodecomposition during exposure and/or thermal decomposition during thermal curing, and these act as a cross-linking catalyst during thermal curing to suppress reflow at the pattern bottom.

In the negative photosensitive resin composition of the present invention, the content ratio of (C1-1) the specific oxime ester photopolymerization initiator in the (C1) photopolymerization initiator is preferably 55% by mass or more, and 60% by mass. % or more, more preferably 65 mass % or more, even more preferably 70 mass % or more, and particularly preferably 75 mass % or more. When the content ratio is 55% by mass or more, the sensitivity during exposure can be improved, and the change in pattern opening dimension width before and after heat curing can be suppressed. On the other hand, the content ratio of the specific oxime ester photopolymerization initiator (C1-1) is preferably 95% by mass or less, more preferably 93% by mass or less, further preferably 90% by mass or less, and further preferably 88% by mass or less. More preferably, 85% by mass or less is particularly preferable. When the content ratio is 95% by mass or less, the sensitivity during exposure can be improved, and the change in pattern opening dimension width before and after heat curing can be suppressed.

In the negative photosensitive resin composition of the present invention, (C1-2) an α-aminoketone-based photopolymerization initiator, (C1-3) an acylphosphine oxide-based photopolymerization initiator and (C1-4) The total content of the biimidazole-based photopolymerization initiator is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, and even more preferably 12% by mass or more. , 15% by mass or more is particularly preferred. When the content ratio is 5% by mass or more, the sensitivity during exposure can be improved, and the change in the pattern opening dimension width before and after heat curing can be suppressed. On the other hand, the content ratio of the specific oxime ester photopolymerization initiator (C1-1) is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and further preferably 30% by mass or less. More preferably, 25% by mass or less is particularly preferable. When the content ratio is 45% by mass or less, the sensitivity during exposure can be improved, and the change in pattern opening dimension width before and after heat curing can be suppressed.

<(C2) Photoacid generator>
The negative photosensitive resin composition of the present invention may further contain (C2) a photoacid generator as (C) a photosensitive agent. (C2) Photoacid generator refers to a compound that causes bond cleavage upon exposure to generate an acid. By including (C2) a photoacid generator, UV curing during exposure is accelerated, and sensitivity can be improved. In addition, the crosslink density of the resin composition after thermosetting is improved, and the chemical resistance of the cured film can be improved. (C2) Photoacid generators include ionic compounds and nonionic compounds.

As the ionic compound (C2) photoacid generator, those containing no heavy metals or halogen ions are preferred, and triorganosulfonium salt compounds are more preferred. Triorganosulfonium salt compounds include, for example, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, or 4-toluenesulfonate of triphenylsulfonium; methanesulfonic acid of dimethyl-1-naphthylsulfonium salt, trifluoromethanesulfonate, camphorsulfonate or 4-toluenesulfonate; dimethyl(4-hydroxy-1-naphthyl)sulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate or 4-toluenesulfonate; dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, or 4-toluenesulfonate; diphenyliodonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, or 4-toluenesulfonate.

Examples of the nonionic compound (C2) photoacid generator include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, carboxylate ester compounds, sulfonimide compounds, phosphate ester compounds, or sulfonebenzotriazoles. compound. Among these (C2) photoacid generators, nonionic compounds are more preferable than ionic compounds from the viewpoint of solubility and insulating properties of the cured film. From the viewpoint of the strength of the generated acid, those that generate benzenesulfonic acid, 4-toluenesulfonic acid, perfluoroalkylsulfonic acid, or phosphoric acid are more preferable. From the viewpoint of high sensitivity due to high quantum yield to j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) and transparency of the cured film, sulfone More preferred are acid ester compounds, sulfonimide compounds and iminosulfonate compounds.

The content of the photoacid generator (C2) in the negative photosensitive resin composition of the present invention is 0 when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. 0.1 parts by mass or more is preferred, 0.5 parts by mass or more is more preferred, 0.7 parts by mass or more is even more preferred, and 1 part by mass or more is particularly preferred. When the content is 0.1 part by mass or more, the sensitivity during exposure can be improved. On the other hand, the content of the (C2) photoacid generator is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is 25 parts by mass or less, the resolution after development can be improved, and a pattern shape with a low taper can be obtained.

<(D) Coloring Agent, (Da) Blacking Agent, and (Db) Non-Black Coloring Agent>
The negative photosensitive resin composition of the present invention further contains (Da) a black agent as (D) a colorant. (D) The coloring agent is a compound that absorbs light of a specific wavelength, and particularly refers to a compound that colors by absorbing light of a visible wavelength (380 to 780 nm). (D) By containing a coloring agent, the film obtained from the negative photosensitive resin composition can be colored, and the light transmitted through the film of the resin composition or the light reflected from the film of the resin composition can be imparted with a coloring property to be colored in a desired color. In addition, it is possible to impart a light-shielding property of shielding light having a wavelength absorbed by the (D) colorant from light transmitted through the film of the resin composition or light reflected from the film of the resin composition.

(D) Colorants include compounds that absorb visible light wavelengths and are colored red, orange, yellow, green, blue, or purple. By combining two or more of these colorants, the light transmitted through the film of the resin composition or the light reflected from the film of the resin composition is toned to the desired color coordinates, and the toning property is improved. be able to.

The negative photosensitive resin composition of the present invention contains (D) a colorant and (Da) a black agent as essential components. (Da) The black agent refers to a compound that is colored black by absorbing light of visible light wavelengths. (Da) Inclusion of a black agent causes the film of the resin composition to be blackened, so that light passing through the film of the resin composition or light reflected from the film of the resin composition is blocked. can be improved. Therefore, a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, Suitable for applications such as color filters, black matrices or black column spacers. In particular, a pixel division layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, a TFT protective layer, an electrode protective layer, and a wiring having a light-shielding property of an organic EL display. It is preferable as a protective layer or a gate insulating layer, and is suitable for applications that require high contrast by suppressing external light reflection, such as a pixel division layer, an interlayer insulating layer, a TFT flattening layer, or a TFT protective layer having a light shielding property. be.

(D) The black color in the colorant means that the Color Index Generic Name (hereinafter referred to as "C.I. number") includes "BLACK". C. I. Those not given a number are black when cured. Two or more C.I. I. (D) a mixture of colorants whose numbers are not black; and C. I. Black in a mixture of two or more (D) colorants containing at least one unnumbered (D) colorant means that the cured film is black. The black color in the case of a cured film is the transmittance per 1.0 μm film thickness at a wavelength of 550 nm in the transmission spectrum of the cured film of the resin composition containing the (D) colorant, based on the Lambert-Beer equation. Therefore, when the film thickness is converted within the range of 0.1 to 1.5 μm so that the transmittance at a wavelength of 550 nm is 10%, the transmittance at a wavelength of 450 to 650 nm in the converted transmission spectrum is 25. % or less.

The transmission spectrum of the cured film can be obtained by the following method. A resin composition containing at least an arbitrary binder resin and (D) colorant is prepared so that the content of (D) colorant in the total solid content of the resin composition is 35% by mass. After coating a film of the resin composition on a Tempax glass substrate (manufactured by AGC Techno Glass), the film is prebaked at 110° C. for 2 minutes to form a prebaked film. Next, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), heat curing is performed at 250 ° C. for 60 minutes in a nitrogen atmosphere, and (D) the film thickness of the resin composition containing the coloring agent. A 1.0 μm cured film (hereinafter referred to as “colorant-containing cured film”) is prepared. Alternatively, a resin composition containing the binder resin and not containing (D) a coloring agent is prepared, coated, pre-baked and heat-cured on a Tempax glass substrate in the same manner as described above, and (D) colored. A cured film having a film thickness of 1.0 μm (hereinafter referred to as “blank cured film”) is prepared from a resin composition containing no agent. Using an ultraviolet-visible spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation), first, a Tempax glass substrate on which a blank cured film was formed to a thickness of 1.0 μm was measured, and the ultraviolet-visible absorption spectrum was measured as that of the blank. do. Next, the Tempax glass substrate on which the prepared colorant-containing cured film was formed was measured with a single beam, and the transmittance per 1.0 μm film thickness at a wavelength of 450 to 650 nm was obtained. Calculate the transmittance of the cured film.

(Da) As the black agent, from the viewpoint of light-shielding properties, a compound that absorbs light of all wavelengths of visible light and is colored black is preferable. Also preferred are mixtures of two or more (D) colorants selected from red, orange, yellow, green, blue or violet colorants. By combining two or more colors of these coloring agents (D), a pseudo-black color can be obtained, and light-shielding properties can be improved.

(Da) The maximum transmission wavelength of the black agent is preferably 330 nm or longer, more preferably 340 nm or longer, and even more preferably 350 nm or longer. When the maximum transmission wavelength is 330 nm or more, the sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. On the other hand, (Da) the maximum transmission wavelength of the black agent is preferably 410 nm or less, more preferably 400 nm or less, still more preferably 390 nm or less, and particularly preferably 380 nm or less. When the maximum transmission wavelength is 410 nm or less, the sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics.

Further, as described above, when the maximum transmission wavelength of (Da) the black agent is 330 to 410 nm, the maximum absorption wavelength of the above-mentioned (C1-1) specific oxime ester photopolymerization initiator is 330 to 410 nm. Preferably.

(D) The maximum transmission wavelength of the coloring agent is determined by measuring the transmittance per 1.0 μm film thickness at a wavelength of 300 to 800 nm in the same manner as the method for measuring the transmission spectrum of the cured film described above, and measuring the wavelength within the range of 300 to 800 nm. can be calculated by finding the wavelength at which the transmission spectrum exhibits the maximum transmission.

In the negative photosensitive resin composition of the present invention, the above-described (Da) black agent is composed of (D1a) a black pigment, (D2a-1) a black dye, and (D2a-2) a mixture of two or more dyes, which will be described later. It is preferable to contain one or more selected types, and from the viewpoint of light-shielding properties, it is more preferable to contain (D1a) a black pigment, which will be described later.

(Db) The coloring agent other than black refers to a compound that is colored by absorbing light with a wavelength of visible light. That is, it is a coloring agent that colors red, orange, yellow, green, blue, or purple, excluding black, as described above. By containing (Da) a black agent and (Db) a coloring agent other than black, light-shielding properties and coloring properties and/or toning properties can be imparted to the film of the resin composition.

In the negative photosensitive resin composition of the present invention, the above-mentioned (Db) coloring agent other than black preferably contains (D1b) a pigment other than black and/or (D2b) a dye other than black described later. , from the viewpoint of light-shielding property and heat resistance or weather resistance, it is more preferable to contain (D1b) a pigment other than black, which will be described later.

In the negative photosensitive resin composition of the present invention, the content ratio of (D) colorant to 100% by mass of the total of (A) alkali-soluble resin, (D) colorant, and (E) dispersant described later is 15% by mass or more is preferable, 20% by mass or more is more preferable, 25% by mass or more is still more preferable, and 30% by mass or more is particularly preferable. When the content ratio is 15% by mass or more, it is possible to improve light shielding properties, coloring properties, or toning properties. On the other hand, the content of the (D) colorant is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% by mass or less. When the content ratio is 80% by mass or less, the sensitivity during exposure can be improved.

In addition, the content ratio of the (D) colorant in the total solid content of the negative photosensitive resin composition of the present invention excluding the solvent is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass. % or more is more preferable, and 20% by mass or more is particularly preferable. When the content is 5% by mass or more, it is possible to improve light shielding properties, coloring properties, or toning properties. On the other hand, the content ratio of the (D) colorant is preferably 70% by mass or less, more preferably 65% by mass or less, even more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly 50% by mass or less. preferable. When the content ratio is 70% by mass or less, the sensitivity during exposure can be improved.

In the negative photosensitive resin composition of the present invention, the preferred content ratio of (Da) the black agent is the same as the preferred content ratio of the (D) colorant described above.

<(D1) Pigment, (D1-1) Organic Pigment, and (D1-2) Inorganic Pigment>
In the negative photosensitive resin composition of the present invention, it is preferable that the above-described (D) colorant contains (D1) a pigment. As a mode in which the above-described (D) colorant contains (D1) a pigment, the above-described (Da) black agent must be included, and (Db) a colorant other than black can be optionally included. (D1) pigment refers to a compound that colors an object by physical adsorption of (D1) pigment on the surface of the object, or interaction between the surface of the object and (D1) pigment. , generally insoluble in solvents and the like. In addition, the coloration by the (D1) pigment has a high concealing property and is resistant to fading due to ultraviolet rays or the like. By including the pigment (D1), the resin composition can be colored in a color having excellent hiding properties, and the light-shielding properties and weather resistance of the film of the resin composition can be improved.

The number average particle diameter of the pigment (D1) is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, even more preferably 10 to 200 nm. When the number average particle diameter of the (D1) pigment is from 1 to 1,000 nm, the light-shielding property of the film of the resin composition and the dispersion stability of the (D1) pigment can be improved. Here, the number average particle diameter of the (D1) pigment is measured by a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter) or a zeta potential/particle size/molecular weight measuring device (Zetasizer Nano ZS; Sysmex Co., Ltd.). ) and measuring the laser scattering due to the Brownian motion of the (D1) pigment in solution (dynamic light scattering method). Further, the number average particle size of the (D1) pigment in the cured film obtained from the resin composition is measured using a scanning electron microscope (hereinafter, "SEM") and a transmission electron microscope (hereinafter, "TEM"). can be obtained by doing (D1) The number average particle diameter of the pigment is directly measured at a magnification of 50,000 to 200,000 times. (D1) When the pigment is a true sphere, the diameter of the true sphere is measured and taken as the number average particle diameter. (D1) When the pigment is not spherical, the longest diameter (hereinafter referred to as "major axis diameter") and the longest diameter in the direction orthogonal to the major axis diameter (hereinafter referred to as "minor axis diameter") are measured, and the major axis diameter The biaxial average diameter obtained by averaging the minor axis diameter and the minor axis diameter is taken as the number average particle diameter.

Examples of (D1) pigments include (D1-1) organic pigments and (D1-2) inorganic pigments. (D1-1) Organic pigments include, for example, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, thioindigo-based pigments, diketopyrrolopyrrole-based pigments, threne-based pigments, indoline-based pigments, and benzofuranone-based pigments. , perylene pigments, aniline pigments, azo pigments, condensed azo pigments, or carbon black. (D1-2) Inorganic pigments include, for example, graphite, silver-tin alloys, fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver, oxides, Composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides.

Preferred content ratios of (D1) pigment, (D1-1) organic pigment, and (D1-2) inorganic pigment in the total solid content of the negative photosensitive resin composition of the present invention excluding the solvent are as described above. The preferred content ratio of the (D) colorant is as follows.

<(D1a) black pigment and (D1b) non-black pigment>
In the negative photosensitive resin composition of the present invention, the above-mentioned (D1) pigment preferably contains (D1a) a black pigment, or (D1a) a black pigment and (D1b) a pigment other than black.

(D1a) Black pigment refers to a pigment that is colored black by absorbing light with a visible wavelength. By including (D1a) a black pigment, the film of the resin composition is blackened and has excellent hiding properties, so that the light-shielding properties of the film of the resin composition can be improved.

In the negative photosensitive resin composition of the present invention, the above-described (Da) black agent is (D1a) a black pigment, and this (D1a) black pigment is (D1a-1) a black organic pigment (D1a) described later. -2) Black inorganic pigments, and (D1a-3) one or more kinds selected from a mixture of two or more color pigments.

(D1b) A pigment other than black refers to a pigment that absorbs light in the wavelength range of visible light to color the pigment excluding black, violet, blue, green, yellow, orange, or red. (D1b) By containing a pigment other than black, the film of the resin composition can be colored, and coloring or toning properties can be imparted. (D1b) By combining two or more pigments other than black, the film of the resin composition can be toned to desired color coordinates, and toning properties can be improved. (D1b) Non-black pigments include pigments other than black that are colored red, orange, yellow, green, blue, or purple, which will be described later.

In the negative photosensitive resin composition of the present invention, the pigment (D1b) other than black described above is (D1b-1) an organic pigment other than black and/or (D1b-2) an inorganic pigment other than black described later. Preferably.

<(D1a-1) Black Organic Pigment, (D1a-2) Black Inorganic Pigment, and (D1a-3) Two or More Color Pigment Mixture>
In the negative photosensitive resin composition of the present invention, the above-described (D1a) black pigment includes (D1a-1) a black organic pigment, (D1a-2) a black inorganic pigment, and (D1a-3) two or more It is preferably one or more selected from color pigment mixtures.

(D1a-1) The black organic pigment refers to an organic pigment that is colored black by absorbing light of visible light wavelengths. By including (D1a-1) a black organic pigment, the film of the resin composition is blackened and has excellent hiding properties, so that the light-shielding properties of the film of the resin composition can be improved. Furthermore, since it is an organic substance, it is possible to improve the toning property by adjusting the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or blocking light of a desired specific wavelength by chemical structure change or functional conversion. can be done. In addition, (D1a-1) black organic pigment has excellent insulating properties and low dielectric properties compared to general inorganic pigments, so by containing (D1a-1) black organic pigment, the resistance value of the film can be improved. In particular, when it is used as an insulating layer such as a pixel dividing layer of an organic EL display, a TFT flattening layer, or a TFT protective layer, it is possible to suppress light emission defects and improve reliability.

(D1a-1) Black organic pigments include, for example, anthraquinone black pigments, benzofuranone black pigments, perylene black pigments, aniline black pigments, azo black pigments, azomethine black pigments, and carbon black. Carbon blacks include, for example, channel black, furnace black, thermal black, acetylene black, and lamp black. From the viewpoint of light shielding properties, channel black is preferred.

(D1a-2) The black inorganic pigment refers to an inorganic pigment that is colored black by absorbing light in the visible wavelength range. By including (D1a-2) a black inorganic pigment, the film of the resin composition is blackened and has excellent hiding properties, so that the light-shielding properties of the film of the resin composition can be improved. Furthermore, since it is an inorganic substance and is superior in heat resistance and weather resistance, it is possible to improve the heat resistance and weather resistance of the film of the resin composition.

(D1a-2) Black inorganic pigments include, for example, graphite or silver-tin alloys, or fine particles and oxides of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver. , complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides. From the viewpoint of improving the light-shielding property, the (D1a-2) black inorganic pigment is preferably titanium or silver fine particles, oxides, composite oxides, sulfides, nitrides, carbides, or oxynitrides, and titanium nitrides. Or an oxynitride is more preferable.

(D1a-3) A pigment mixture of two or more colors is a pigment that gives a pseudo-black color by combining two or more pigments selected from red, orange, yellow, green, blue, or purple pigments. A mixture. (D1a-3) By containing a mixture of pigments of two or more colors, the film of the resin composition is blackened and has excellent hiding properties, so that the light-shielding properties of the film of the resin composition can be improved. Furthermore, since two or more colors of pigments are mixed, the transmission spectrum or absorption spectrum of the resin composition film can be adjusted, such as by transmitting or blocking light of a desired specific wavelength, and toning properties can be improved.

Known pigments can be used as the black organic pigment, black inorganic pigment, red pigment, orange pigment, yellow pigment, green pigment, blue pigment, and violet pigment.

<(D1b-1) Non-Black Organic Pigment, (D1b-2) Non-Black Inorganic Pigment>
In the negative photosensitive resin composition of the present invention, the (D1b) non-black pigment described above is (D1b-1) a non-black organic pigment and/or (D1b-2) a non-black inorganic pigment. is preferred.

(D1b-1) Organic pigments other than black refer to organic pigments that color red, orange, yellow, green, blue, or purple other than black by absorbing light of visible light wavelengths. (D1b-1) Since the organic pigment other than black is an organic substance, it changes the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or blocking light of a desired specific wavelength by chemical structural change or functional conversion. can be adjusted to improve toning.

(D1b-2) Non-black inorganic pigments refer to inorganic pigments that are colored red, orange, yellow, green, blue, or purple other than black by absorbing light of visible light wavelengths. (D1b-2) The inorganic pigment other than black is an inorganic substance and is superior in heat resistance and weather resistance, and thus can improve the heat resistance and weather resistance of the film of the resin composition.

In the negative photosensitive resin composition of the present invention, (D1b-1) an organic pigment other than black is one selected from the group consisting of a blue pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a green pigment. More than one type is preferred. However, (D1a-3) a mixture of two or more color pigments as the black pigment (D1a) described above is excluded. (D1b-1) When the non-black organic pigment is one or more selected from the group consisting of a blue pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a green pigment, the film of the resin composition is light-shielded. Since the transmittance of wavelengths in the ultraviolet region can be increased while maintaining the properties, the sensitivity at the time of exposure can be improved, and a low tapered pattern can be formed after development. In addition, halftone characteristics can be improved.

Pigments that color blue include, for example, Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, and 64 (all numerical values are C.I. numbers). Pigments coloring red include, for example, Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, or 250 (all numerical values are CI numbers). Pigments coloring yellow include, for example, Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 120, 125, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 166, 168, 175, 180, 181, 185, 192, or 194 (all values are CI numbers). Pigments that color purple include, for example, Pigment Violet 19, 23, 29, 30, 32, 37, 40, and 50 (all numerical values are C.I. numbers). Pigments that color orange include, for example, Pigment Orange 12, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, or 72 (all numerical values are C.I. numbers). . Pigments that color green include, for example, Pigment Green 7, 10, 36, and 58 (all numerical values are C.I. numbers).

From the viewpoints of improving sensitivity during exposure, reducing taper by controlling pattern shape after development, and improving halftone characteristics, (D1b-1) organic pigments other than black include the above-mentioned blue pigments, such as C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, and C.I. I. Pigment Blue 60 is preferably one or more selected from the group consisting of C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179, and C.I. I. Pigment Red 190 is preferably one or more selected from the group consisting of C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 192, and C.I. I. Pigment Yellow 194 is preferably one or more selected from the group consisting of C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 29, and C.I. I. Pigment Violet 37 is preferably one or more selected from the group consisting of C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, and C.I. I. It is preferably one or more selected from the group consisting of Pigment Orange 72 .

In addition, when the organic pigment (D1b-1) other than black has the above-described structure, the heat resistance of the pigment is excellent, the halogen content derived from the pigment in the resin composition can be reduced, and the insulation and low dielectric properties are achieved. Therefore, when used as an insulating layer such as a pixel dividing layer of an organic EL display, a TFT flattening layer, or a TFT protective layer, it is possible to suppress light emission defects and improve reliability.

The content ratio of the organic pigment (D1b-1) other than black in the total solid content of the negative photosensitive resin composition of the present invention excluding the solvent is preferably 1% by mass or more, more preferably 3% by mass or more. , more preferably 5% by mass or more, and particularly preferably 7% by mass or more. When the content is 1% by mass or more, sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, halftone characteristics can be improved. On the other hand, the content ratio of (D1b-1) organic pigment other than black is preferably 25% by mass or less, more preferably 22% by mass or less, even more preferably 20% by mass or less, even more preferably 17% by mass or less, and 15% by mass. % by mass or less is particularly preferred. When the content ratio is 25% by mass or less, the light shielding property and the toning property can be improved.

<(D1a-1a) Benzofuranone Black Pigment, (D1a-1b) Perylene Black Pigment, and (D1a-1c) Azo Black Pigment>
The negative photosensitive resin composition of the present invention is used from the viewpoints of improving the sensitivity during exposure, reducing the taper by controlling the pattern shape after development, suppressing changes in pattern opening dimension width before and after heat curing, and improving halftone characteristics. , The above-mentioned (D1a-1) black organic pigment is one selected from the group consisting of (D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) azo-based black pigment. More than one type is preferable, and (D1a-1a) benzofuranone-based black pigment is more preferable.

(D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) containing one or more selected from the group consisting of azo-based black pigment, thereby forming a resin composition film. is blackened and has excellent hiding properties, so that the light-shielding properties of the film of the resin composition can be improved. In particular, as compared with general organic pigments, the light-shielding property per unit content ratio of the pigment in the resin composition is excellent, so that the same light-shielding property can be imparted with a small content ratio. Therefore, the light shielding property of the film can be improved, and the sensitivity during exposure can be improved. Furthermore, since it is an organic substance, it is possible to improve the toning property by adjusting the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or blocking light of a desired specific wavelength by chemical structure change or functional conversion. can be done. In particular, since the transmittance of wavelengths in the near-infrared region (for example, 700 nm or more) can be improved, it has light-shielding properties and is suitable for applications using light with wavelengths in the near-infrared region. In addition, since it is superior in insulating properties and low dielectric properties compared to general organic pigments and inorganic pigments, it is possible to improve the resistance value of the film. In particular, when it is used as an insulating layer such as a pixel dividing layer of an organic EL display, a TFT flattening layer, or a TFT protective layer, it is possible to suppress light emission defects and improve reliability.

In addition, (D1a-1a) benzofuranone-based black pigment absorbs light with a wavelength of visible light, while having a high transmittance of wavelengths in the ultraviolet region (for example, 400 nm or less). Therefore, (D1a-1a) benzofuranone-based black pigment can improve the sensitivity at the time of exposure, and can form a low tapered pattern after development.

On the other hand, when (D1a-1a) a benzofuranone-based black pigment is contained, as described above, pigment-derived development residues may occur due to insufficient alkali resistance of this pigment. That is, when the surface of the (D1a-1a) benzofuranone-based black pigment described above is exposed to an alkaline developer during development, part of the surface is decomposed or dissolved, and remains on the substrate as a development residue derived from the pigment described above. sometimes. In such a case, as described above, (B3) a flexible chain-containing radically polymerizable compound and (B1) a fluorene skeleton-containing radically polymerizable compound or (B2) an indane skeleton-containing radically polymerizable compound are contained. , it is possible to suppress the generation of development residue derived from the above-mentioned pigment.

(D1a-1a) A benzofuranone-based black pigment has a benzofuran-2(3H)-one structure or a benzofuran-3(2H)-one structure in the molecule, and turns black by absorbing light with a wavelength of visible light. A coloring compound. (D1a-1a) Benzofuranone-based black pigments are preferably benzofuranone compounds represented by any of the general formulas (63) to (68), geometric isomers thereof, salts thereof, or salts of geometric isomers thereof.

In general formulas (63) to (65), R ²⁰⁶ , R ²⁰⁷ , R ²¹² , R ²¹³ , R ²¹⁸ and R ²¹⁹ are each independently hydrogen, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or represents an alkyl group having 1 to 10 carbon atoms and having 1 to 20 fluorine atoms. R ²⁰⁸ , R ²⁰⁹ , R ²¹⁴ , R ²¹⁵ , R ²²⁰ and R ²²¹ are each independently hydrogen, a halogen atom, R ²⁵¹ , COOH, COOR ²⁵¹ , COO ⁻ , CONH ₂ , CONHR ²⁵¹ , CONR ²⁵¹ R ²⁵² , CN, ^{OH , OR251 , OCOR251} , _OCONH2 , ^OCONHR251 , OCONR251R252, _NO2 , _NH2 , ^NHR251 , ^NR251R252 , ^{NHCOR251 , NR251COR252} , N= _CH2 , ^N = ^CHR251 _{, N} = ^CR251R252 , SH, ^SR251 , ^SOR251 , ^SO2R251 , ^SO3R251 , _SO3H , _{SO3- , SO2NH2 ,} ^{SO2NHR251 ,} or SO ₂ NR ²⁵¹ R ²⁵² , wherein R ²⁵¹ and R ²⁵² are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. It represents a 4-10 cycloalkenyl group or a C2-10 alkynyl group. Plural R ²⁰⁸ , R ²⁰⁹ , R ²¹⁴ , R ²¹⁵ , R ²²⁰ or R ²²¹ may be directly bonded or form a ring with oxygen atom bridge, sulfur atom bridge, NH bridge or NR ²⁵¹ bridge. do not have. R ²¹⁰ , R ²¹¹ , R ²¹⁶ , R ²¹⁷ , R ²²² and R ²²³ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a, b, c, d, e, and f each independently represents an integer of 0 to 4; The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aryl group described above may have a heteroatom and may be unsubstituted or substituted.

In general formulas (66) to (68), R ²⁵³ , R ²⁵⁴ , R ²⁵⁹ , R ²⁶⁰ , R ²⁶⁵ and R ²⁶⁶ are each independently hydrogen, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or represents an alkyl group having 1 to 10 carbon atoms and having 1 to 20 fluorine atoms. R ²⁵⁵ , R ²⁵⁶ , R ²⁶¹ , R ²⁶² , R ²⁶⁷ and R ²⁶⁸ are each independently hydrogen, a halogen atom, R ²⁷¹ , COOH, COOR ²⁷¹ , COO ⁻ , CONH ₂ , CONHR ²⁷¹ , CONR ²⁷¹ R ^{272 ,} CN, ^{OH , OR271 , OCOR271} , _OCONH2 , ^OCONHR271 , OCONR271R272, _NO2 , _NH2 , ^NHR271 , ^NR271R272 , ^NHCOR271 , ^NR271COR272 , N= _CH2 , _N = ^CHR271 , N= ^CR271R272 _, SH, ^SR271 , ^{SOR271 , SO2R271} _, ^SO3R271 , _SO3H , _SO3- ^, _{SO2NH2 ,} ^SO2NHR271 , or SO ₂ NR ²⁷¹ R ²⁷² , wherein R ²⁷¹ and R ²⁷² are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. It represents a 4-10 cycloalkenyl group or a C2-10 alkynyl group. Plural R ²⁵⁵ , R ²⁵⁶ , R ²⁶¹ , R ²⁶² , R ²⁶⁷ or R ²⁶⁸ may be directly bonded or form a ring with oxygen atom bridge, sulfur atom bridge, NH bridge or NR ²⁷¹ bridge. do not have. R ²⁵⁷ , R ²⁵⁸ , R ²⁶³ , R ²⁶⁴ , R ²⁶⁹ and R ²⁷⁰ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a, b, c, d, e, and f each independently represents an integer of 0 to 4; The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, and aryl group described above may have a heteroatom and may be unsubstituted or substituted.

(D1a-1a) Benzofuranone-based black pigments include, for example, "IRGAPHOR" (registered trademark) BLACK S0100CF (manufactured by BASF), the black pigment described in International Publication No. 2010/081624, or the black pigment described in International Publication No. 2010/081756. of black pigments.

The (D1a-1b) perylene-based black pigment refers to a compound that has a perylene structure in its molecule and that absorbs light of visible light wavelengths to color it black. (D1a-1b) Perylene-based black pigments are preferably perylene compounds represented by any one of general formulas (69) to (71), geometric isomers thereof, salts thereof, or salts of geometric isomers thereof.

In general formulas (69) to (71), X ⁹² , X ⁹³ , X ⁹⁴ and X ⁹⁵ each independently represent an alkylene chain having 1 to 10 carbon atoms. R ²²⁴ and R ²²⁵ each independently represent hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. R ²⁴⁹ , R ²⁵⁰ and R ²⁵¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms and having 1 to 20 fluorine atoms. R ²⁷³ and R ²⁷⁴ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms. a and b each independently represents an integer of 0 to 5; The alkylene chains, alkoxy groups, acyl groups, and alkyl groups described above may have heteroatoms and may be unsubstituted or substituted.

Examples of (D1a-1b) perylene-based black pigments include Pigment Black 31 or 32 (both numerical values are CI numbers). In addition to the above, "PALIOGEN" (registered trademark) BLACK S0084, K0084, L0086, K0086, EH0788, or FK4281 (all manufactured by BASF) can be used.

(D1a-1c) Azo-based black pigment refers to a compound having an azo group in the molecule and coloring black by absorbing light of visible light wavelengths. (D1a-1c) As the azo black pigment, an azo compound represented by the general formula (72) is preferable.

In general formula (72), X ⁹⁶ represents an arylene chain having 6 to 15 carbon atoms. Y ⁹⁶ represents an arylene chain with 6 to 15 carbon atoms. R ²⁷⁵ , R ²⁷⁶ and R ²⁷⁷ each independently represent a halogen or an alkyl group having 1 to 10 carbon atoms. R ²⁷⁸ represents a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a nitro group. R ²⁷⁹ represents a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acylamino group having 2 to 10 carbon atoms, or a nitro group. R ²⁸⁰ , R ²⁸¹ , R ²⁸² and R ²⁸³ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 4, b represents an integer of 0 to 2, c represents an integer of 0 to 4, and d and e each independently represent an integer of 0 to 8. , n represents an integer of 1 to 4. The arylene chain, alkyl group, alkoxy group, and acylamino group described above may have a heteroatom and may be unsubstituted or substituted.

(D1a-1c) Azo black pigments include, for example, "CHROMOFINE" (registered trademark) BLACK A1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.), black pigments described in JP-A-01-170601, or JP-A-02 The black pigments described in JP-A-034664 can be mentioned.

(D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) azo-based black, which account for the total solid content of the negative photosensitive resin composition of the present invention, excluding the solvent The content of one or more pigments selected from the group consisting of pigments is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. When the content ratio is 5% by mass or more, the light shielding property and the toning property can be improved. On the other hand, the content ratio of one or more types selected from the group consisting of (D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) azo-based black pigment is 70% by mass or less. is preferable, 65% by mass or less is more preferable, 60% by mass or less is even more preferable, 55% by mass or less is even more preferable, and 50% by mass or less is particularly preferable. When the content ratio is 70% by mass or less, the sensitivity during exposure can be improved.

<(D1a-3a) a blue pigment, a red pigment, and a coloring pigment mixture containing a yellow pigment, (D1a-3b) a coloring pigment mixture containing a purple pigment and a yellow pigment, (D1a-3c) a blue pigment, a red pigment, and an orange A colored pigment mixture containing a pigment, and (D1a-3d) a colored pigment mixture containing a blue pigment, a purple pigment, and an orange pigment>
As the negative photosensitive resin composition of the present invention, the above-mentioned (D1a-3) a pigment mixture of two or more colors is (D1a-3a) a colored pigment mixture containing a blue pigment, a red pigment, and a yellow pigment, (D1a -3b) a colored pigment mixture containing a purple pigment and a yellow pigment, (D1a-3c) a colored pigment mixture containing a blue pigment, a red pigment and an orange pigment, or (D1a-3d) a blue pigment, a purple pigment and an orange pigment It is preferably a colored pigment mixture containing

(D1a-3) When the pigment mixture of two or more colors has the above-described structure, the film of the resin composition turns black and has excellent hiding properties, so that the light-shielding properties of the film of the resin composition can be improved. . In addition, since the transmittance of wavelengths in the ultraviolet region can be increased, sensitivity during exposure can be improved, and a low tapered pattern can be formed after development. In addition, it is possible to suppress the change in the width of the pattern opening before and after heat curing, and to improve the halftone characteristics. Further, since the transmittance of wavelengths in the near-infrared region can be improved, it has a light-shielding property and is suitable for applications using light with wavelengths in the near-infrared region.

Pigments that color blue include, for example, Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, and 64 (all numerical values are C.I. numbers). Pigments coloring red include, for example, Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, or 250 (all numerical values are CI numbers). Pigments coloring yellow include, for example, Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 120, 125, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 166, 168, 175, 180, 181, 185, 192, or 194 (all values are CI numbers). Pigments that color purple include, for example, Pigment Violet 19, 23, 29, 30, 32, 37, 40, and 50 (all numerical values are C.I. numbers). Pigments that color orange include, for example, Pigment Orange 12, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, or 72 (all numerical values are C.I. numbers). . Pigments that color green include, for example, Pigment Green 7, 10, 36, and 58 (all numerical values are C.I. numbers).

As the negative photosensitive resin composition of the present invention, in the above-mentioned (D1a-3) two or more color pigment mixture, the above-mentioned blue pigment is C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, and C.I. I. Pigment Blue 60 is preferably one or more selected from the group consisting of C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179, and C.I. I. Pigment Red 190 is preferably one or more selected from the group consisting of C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 192, and C.I. I. Pigment Yellow 194 is preferably one or more selected from the group consisting of C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 29, and C.I. I. Pigment Violet 37 is preferably one or more selected from the group consisting of C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, and C.I. I. It is preferably one or more selected from the group consisting of Pigment Orange 72 .

(D1a-3) When the two-color or more pigment mixture has the above structure, the pigment has excellent alkali resistance, so decomposition or dissolution of the pigment surface is suppressed during alkaline development, and the generation of development residue caused by the pigment is suppressed. be able to. In addition, the heat resistance of the pigment is excellent, the halogen content derived from the pigment in the resin composition can be reduced, and the insulation and low dielectric properties are excellent, so that the resistance value of the film can be improved. In particular, when it is used as an insulating layer such as a pixel dividing layer of an organic EL display, a TFT flattening layer, or a TFT protective layer, it is possible to suppress light emission defects and improve reliability.

The content ratio of the two or more color pigment mixture (D1a-3) in the total solid content of the negative photosensitive resin composition of the present invention excluding the solvent is preferably 5% by mass or more, and more preferably 10% by mass or more. It is preferably 15% by mass or more, and particularly preferably 20% by mass or more. When the content ratio is 5% by mass or more, the light shielding property and the toning property can be improved. On the other hand, the content ratio of (D1a-3) two or more color pigment mixture is preferably 70% by mass or less, more preferably 65% by mass or less, further preferably 60% by mass or less, and even more preferably 55% by mass or less, 50% by mass or less is particularly preferred. When the content ratio is 70% by mass or less, the sensitivity during exposure can be improved.

<(DC) coating layer>
In the negative photosensitive resin composition of the present invention, the (D1a-1) black organic pigment preferably further contains (DC) a coating layer. The (DC) coating layer is, for example, a surface treatment with a silane coupling agent, a surface treatment with a silicate, a surface treatment with a metal alkoxide, or a coating treatment with a resin. layer.

(DC) By including a coating layer, the particle surface of the black organic pigment (D1a-1) is acidified, basicized, hydrophilicized, or hydrophobicized to modify the surface state of the particles. It is possible to improve acid resistance, alkali resistance, solvent resistance, dispersion stability or heat resistance. As a result, generation of development residue derived from the pigment can be suppressed. In addition, side etching during development is suppressed, making it possible to form a pattern with a low taper shape after development. change can be suppressed. In addition, it is possible to form a pattern with a low taper shape by controlling the pattern shape after development, so that halftone characteristics can be improved. Further, by forming an insulating coating layer on the surface of the particles, the insulating properties of the cured film can be improved, and the leakage current can be reduced, thereby improving the reliability of the display.

As the (D1a-1) black organic pigment, particularly when (D1a-1a) a benzofuranone-based black pigment is included, the (D1a-1a) benzofuranone-based black pigment is provided with a (DC) coating layer to obtain the pigment The alkali resistance of the pigment can be improved, and the generation of development residue derived from the pigment can be suppressed.

The average coverage of the (DC) coating layer with respect to the black organic pigment (D1a-1) is preferably 50% or more, preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the average coverage of the (DC) coating layer is 80% or more, the generation of residues during development can be suppressed.

The average coverage of the (DC) coating layer with respect to the (D1a-1) black organic pigment is measured using a transmission electron microscope (H9500; manufactured by Hitachi High-Technologies Corporation) under conditions of an acceleration voltage of 300 kV and magnification. Observe the cross section with 50,000 to 200,000 times, and for 100 randomly selected black pigment particles, obtain the coverage M (%) of each black pigment by the following formula, and calculate the number average value By calculating, the average coverage N (%) can be obtained.
Coverage M (%) = {L1/(L1 + L2)} x 100
L1: Total length (nm) of the part covered with the coating layer in the circumference of the particle
L2: The total length (nm) of the portion of the outer periphery of the particle that is not covered with the coating layer (the portion where the interface and the embedding resin are in direct contact)
L1+L2: Perimeter length of particle (nm).

<(DC-1) Silica Coating Layer, (DC-2) Metal Oxide Coating Layer and (DC-3) Metal Hydroxide Coating Layer>
The (DC) coating layer contains one selected from the group consisting of (DC-1) a silica coating layer, (DC-2) a metal oxide coating layer and (DC-3) a metal hydroxide coating layer. is preferred. Since silica, metal oxides and metal hydroxides have the function of imparting alkali resistance to pigments, they can suppress the generation of development residues derived from pigments.

(DC-1) Silica contained in the silica coating layer is a general term for silicon dioxide and its hydrated substances. (DC-2) The metal oxide contained in the metal oxide coating layer is a general term for metal oxides and their hydrates. An example of a metal oxide is alumina, such as alumina (Al ₂ O ₃ ) or alumina hydrate (Al ₂ O _{3.nH 2} O). (DC-3) Examples of the metal hydroxide contained in the metal hydroxide coating layer include aluminum hydroxide (Al(OH) ₃ ). Since silica has a low dielectric constant, even when the (D1a-1) black organic pigment (DC) coating layer contains a large amount of silica, it is possible to suppress an increase in the dielectric constant of the pixel dividing layer.

The (DC-1) silica coating layer, (DC-2) metal oxide coating layer and (DC-3) metal hydroxide coating layer of the (DC) coating layer are analyzed by, for example, X-ray diffraction. be able to. Examples of the X-ray diffractometer include a powder X-ray diffractometer (manufactured by Mac Science). The mass of silicon atoms or metal atoms contained in (DC-1) silica coating layer, (DC-2) metal oxide coating layer and (DC-3) metal hydroxide coating layer is rounded to the second decimal place. to calculate the value to the first decimal place. Further, the mass of the pigment particles excluding the (DC) coating layer contained in the (D1a-1) black organic pigment having the (DC) coating layer can be determined, for example, by the following method. The pigment whose mass was measured is placed in a mortar and ground with a pestle (DC) to remove the coating layer, and then immersed in an amide solvent such as N,N-dimethylformamide to dissolve only the pigment particles and obtain a filtrate. After repeating the removal operation until the blackness of the filtered matter completely disappears, the mass of the filtered matter is measured, and the weight of the pigment is calculated from the difference.

The metal oxide or metal hydroxide contained in the (DC-2) metal oxide coating layer or (DC-3) metal hydroxide coating layer has chemical durability such as alkali resistance, heat resistance and light resistance. It is preferable to have both Vickers hardness capable of withstanding the input of mechanical energy appropriately optimized in the dispersing process and physical durability such as abrasion resistance. Examples of metal oxides and metal hydroxides include alumina, zirconia, zinc oxide, titanium oxide and iron oxide. Alumina or zirconia is preferable from the viewpoint of insulation, ultraviolet transmittance and near-infrared transmittance, and alumina is more preferable from the viewpoint of dispersibility in alkali-soluble resins and solvents. The metal oxide and metal hydroxide may be surface-modified with a group containing an organic group.

When the (DC) coating layer contains a (DC-1) silica coating layer, an alumina coating layer is formed as a (DC-2) metal oxide coating layer on the surface of the (DC-1) silica coating layer. Thereby, deterioration of pattern linearity can be suppressed. Alumina is effective in improving the dispersibility in the aqueous pigment suspension even in the process of sizing the pigment after the surface treatment process of the pigment, so the secondary aggregate particle size can be adjusted within the desired range. Furthermore, productivity and quality stability can be improved. As the (DC-2) metal oxide coating layer contained in the (DC) coating layer, the coating amount of the alumina coating layer is 10 parts by mass when the silica contained in the (DC-1) silica coating layer is 100 parts by mass. 1 part or more is preferable, and 20 parts by mass or more is more preferable.

When the (DC) coating layer contains the (DC-1) silica coating layer, the content of silica is preferably 1 part by mass or more, more preferably 2 parts by mass or more, when the pigment particles are 100 parts by mass. Preferably, 5 parts by mass or more is more preferable. By setting the content to 1 part by mass or more, it is possible to increase the coverage of the particle surface with the pigment and suppress the development residue derived from the pigment. On the other hand, the content of silica is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. By setting the content to 20 parts by mass or less, the pattern linearity of the pixel dividing layer can be improved.

When the (DC) coating layer contains (DC-2) a metal oxide coating layer and/or (DC-3) a metal hydroxide coating layer, the total content of the metal oxide and metal hydroxide is When the pigment particles are 100 parts by mass, the amount is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more. Dispersibility and pattern linearity can be improved by setting the total content to 0.1 parts by mass or more. On the other hand, the total content of metal oxides and metal hydroxides is preferably 15 parts by mass or less, more preferably 10 parts by mass or less. By setting the total content to 15 parts by mass or less, the photosensitive composition of the present invention, which is designed to have a low viscosity, preferably a viscosity of 15 mPa s or less, can generate a concentration gradient of the pigment. can be suppressed, and the storage stability of the coating liquid can be improved.

The content of silica is calculated from the silicon atom content, including cases where it does not become a single component in the interior and surface layers of the (DC) coating layer, and cases where there is a difference in the amount of dehydration due to heat history. It is a value converted to silicon dioxide, and refers to a value converted to _SiO2 . The contents of metal oxides and metal hydroxides refer to metal oxide and metal hydroxide conversion values calculated from metal atom contents. That is, in the case of alumina, zirconia, and titanium oxide, they refer to Al ₂ O ₃ conversion values, ZrO ₂ conversion values, and TiO ₂ conversion values, respectively. In addition, the total content of metal oxides and metal hydroxides refers to the content when either metal oxides or metal hydroxides are included, and the total content when both are included. say.

As the (DC) coating layer, silica, metal oxide or metal water contained in (DC-1) silica coating layer, (DC-2) metal oxide coating layer or (DC-3) metal hydroxide coating layer The surface of the oxide may be modified with an organic group using a silane coupling agent using the hydroxy on the surface of the oxide as a reaction point. As the organic group, an ethylenically unsaturated double bond group is preferred. By modifying the surface with a silane coupling agent having an ethylenically unsaturated double bond group, it is possible to impart radical polymerizability to the black organic pigment (D1a-1) and suppress peeling of the film in the cured portion. , the generation of development residue derived from the pigment in the unexposed area can be suppressed.

In the case of (D1a-1) black organic pigment having a (DC) coating layer, the outermost layer may be further surface-treated with an organic surface treatment agent. By surface-treating the outermost layer, the wettability to the resin or solvent can be improved. The (DC) coating layer may further contain a resin coating layer formed by coating treatment with a resin. By containing the resin coating layer, the surface of the particles is coated with an insulating resin having low conductivity, the surface state of the particles can be modified, and the light shielding properties and insulating properties of the cured film can be improved. .

<(D2) Dye>
In the negative photosensitive resin composition of the present invention, the (D) colorant described above preferably contains (D2) a dye. As a mode in which the above-mentioned (D) coloring agent contains (D2) dye, it is preferable that (D2) dye is contained as the above-mentioned (Da) black agent and/or (Db) coloring agent other than black. .

(D2) The dye is a compound that colors the object by chemically adsorbing or strongly interacting with the surface structure of the object, such as an ionic group or a substituent such as a hydroxy group in the dye (D2). It is generally soluble in solvents and the like. In addition, (D2) coloring with a dye has high coloring power and high coloring efficiency because each molecule adsorbs to an object.

(D2) By containing a dye, it is possible to give a color having excellent coloring power, and it is possible to improve the coloring property and toning property of the film of the resin composition. (D2) Dyes include, for example, direct dyes, reactive dyes, sulfur dyes, vat dyes, acid dyes, metallized dyes, metallized acid dyes, basic dyes, mordant dyes, acid mordant dyes, disperse dyes, and cationic dyes. , or fluorescent brightening dyes. Here, disperse dyes refer to dyes that are insoluble or sparingly soluble in water and do not have anionic ionizable groups such as sulfonic acid groups and carboxyl groups.

(D2) Dyes include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, and threne dyes. , perinone dyes, perylene dyes, triarylmethane dyes, or xanthene dyes. Anthraquinone-based dyes, azo-based dyes, azine-based dyes, methine-based dyes, triarylmethane-based dyes, and xanthene-based dyes are preferred from the viewpoint of solubility in solvents and heat resistance described later.

In the negative photosensitive resin composition of the present invention, the above-described (D2) dye includes (D2a-1) a black dye, (D2a-2) a mixture of two or more dyes, and (D2b) a dye other than black. It is preferable to contain one or more kinds selected from dyes.

The content ratio of the dye (D2) in the total solid content of the negative photosensitive resin composition of the present invention excluding the solvent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0 0.1% by mass or more is more preferable. When the content ratio is 0.01% by mass or more, it is possible to improve the coloring property or the toning property. On the other hand, the content ratio of the dye (D2) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. When the content is 50% by mass or less, the heat resistance of the cured film can be improved.

<(D2a-1) a black dye, (D2a-2) a mixture of two or more dyes, and (D2b) a dye other than black>
In the negative photosensitive resin composition of the present invention, the above-mentioned (D2) dye is composed of (D2a-1) a black dye, (D2a-2) a mixture of two or more dyes, and (D2b) a dye other than black. It is preferable to contain one or more selected types.

(D2a-1) The black dye refers to a dye that turns black by absorbing light of visible light wavelengths. By including (D2a-1) a black dye, the film of the resin composition is blackened and has excellent colorability, so that the light-shielding property of the film of the resin composition can be improved.

(D2a-2) A dye mixture of two or more colors is a combination of two or more dyes selected from white, red, orange, yellow, green, blue, or purple dyes to give a pseudo-black color. , refers to the dye mixture. (D2a-2) By containing a mixture of dyes of two or more colors, the film of the resin composition is blackened and has excellent colorability, so that the light-shielding property of the film of the resin composition can be improved. Furthermore, since two or more dyes are mixed, the transmission spectrum or absorption spectrum of the film of the resin composition can be adjusted, such as transmitting or blocking light of a desired specific wavelength, and the toning properties can be improved. Known dyes can be used as the black dye, red dye, orange dye, yellow dye, green dye, blue dye, and purple dye.

(D2b) A dye other than black refers to a dye that colors white, red, orange, yellow, green, blue, or purple other than black by absorbing light in the wavelength of visible light. (D2b) By containing a dye other than black, the film of the resin composition can be colored, and coloring or toning properties can be imparted. (D2b) By combining two or more dyes other than black, the film of the resin composition can be toned to desired color coordinates, and toning properties can be improved. (D2b) Dyes other than black include the above-described dyes other than black that color white, red, orange, yellow, green, blue, or purple.

The cured film obtained by curing the negative photosensitive resin composition in the present invention preferably has an optical density of 0.3 or more, more preferably 0.5 or more, in the visible light region per 1 μm of film thickness. It is preferably 0.7 or more, and particularly preferably 1.0 or more. The visible light region has a wavelength of about 400 to 700 nm. When the optical density per 1 μm of the film thickness is 0.3 or more, the cured film can improve the light shielding property, so in a display device such as an organic EL display or a liquid crystal display, it is possible to prevent the electrode wiring from becoming visible or to reflect external light. reduction is possible, and the contrast in image display can be improved. Therefore, a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, Suitable for applications such as color filters, black matrices, or black column spacers. In particular, a pixel division layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, a TFT protective layer, an electrode protective layer, and a wiring having a light-shielding property of an organic EL display. It is preferable as a protective layer or a gate insulating layer, and is suitable for applications that require high contrast by suppressing external light reflection, such as a pixel division layer, an interlayer insulating layer, a TFT flattening layer, or a TFT protective layer having a light shielding property. be. On the other hand, the optical density per 1 μm of film thickness is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. When the optical density per 1 μm of the film thickness is 5.0 or less, the sensitivity at the time of exposure can be improved, and a cured film having a pattern shape with a low taper can be obtained. The optical density per 1 μm of film thickness of the cured film can be adjusted by the composition and content ratio of the colorant (D) described above.

<(E) Dispersant>
The negative photosensitive resin composition of the present invention preferably further contains (E) a dispersant. (E) The dispersing agent includes a surface affinity group that interacts with the surface such as a disperse dye as the (D1) pigment and / or (D2) dye described above, and a dispersing group as (D1) the pigment and / or (D2) dye A compound having a dispersion stabilizing structure that improves the dispersion stability of a dye. (E) The dispersion stabilizing structure of the dispersant includes a polymer chain and/or a substituent having an electrostatic charge.

By containing (E) a dispersant, when the negative photosensitive resin composition contains disperse dyes as (D1) pigments and/or (D2) dyes, their dispersion stability can be improved. , the resolution after development can be improved. In particular, for example, when the (D1) pigment is a particle crushed to a number average particle diameter of 1 μm or less, the surface area of the (D1) pigment particles increases, so the (D1) pigment particles tend to aggregate. Become. On the other hand, when (E) a dispersant is contained, the surface of the crushed (D1) pigment interacts with the surface affinity group of (E) the dispersant, and (E) the dispersion stabilization of the dispersant The steric hindrance and/or electrostatic repulsion due to the structure can inhibit the aggregation of the (D1) pigment particles and improve the dispersion stability.

Examples of the (E) dispersant having a surface affinity group include (E) a dispersant having only basic groups, (E) dispersing agents having both basic and acidic groups, and (E) having only acidic groups. Dispersants or (E) dispersants having neither basic groups nor acidic groups are included. (D1) From the viewpoint of improving the dispersion stability of the pigment particles, the (E) dispersant having only basic groups and the (E) dispersant having both basic and acidic groups are preferred. Moreover, it is also preferable that the basic group and/or the acidic group, which are the surface affinity groups, have a structure in which a salt is formed with an acid and/or a base.

(E) The basic group of the dispersant or the structure formed by forming a salt of the basic group includes a tertiary amino group, a quaternary ammonium salt structure, a pyrrolidine skeleton, a pyrrole skeleton, an imidazole skeleton, a pyrazole skeleton, a triazole skeleton, Tetrazole skeleton, imidazoline skeleton, oxazole skeleton, isoxazole skeleton, oxazoline skeleton, isoxazoline skeleton, thiazole skeleton, isothiazole skeleton, thiazoline skeleton, isothiazoline skeleton, thiazine skeleton, piperidine skeleton, piperazine skeleton, morpholine skeleton, pyridine skeleton, pyridazine skeleton , a pyrimidine skeleton, a pyrazine skeleton, a triazine skeleton, an isocyanuric acid skeleton, an imidazolidinone skeleton, a propylene urea skeleton, a butylene urea skeleton, a hydantoin skeleton, a barbituric acid skeleton, an alloxane skeleton or a nitrogen-containing ring skeleton such as a glycoluril skeleton. .

From the viewpoint of improving the dispersion stability and improving the resolution after development, the basic group or the structure in which the basic group forms a salt includes a tertiary amino group, a quaternary ammonium salt structure, a pyrrole skeleton, an imidazole skeleton, and a pyrazole skeleton. , a pyridine skeleton, a pyridazine skeleton, a pyrimidine skeleton, a pyrazine skeleton, a triazine skeleton, an isocyanuric acid skeleton, an imidazolidinone skeleton, a propylene urea skeleton, a butylene urea skeleton, a hydantoin skeleton, a barbituric acid skeleton, an alloxane skeleton or a glycoluril skeleton. A nitrogen ring skeleton is preferred.

(E) dispersants having only basic groups include, for example, "DISPERBYK" (registered trademark) -108, -160, -167, -182, -2000, or -2164, "BYK" (registered trademark) -9075, -LP-N6919, or -LP-N21116 (both of which are manufactured by BYK Chemie Japan), "EFKA" (registered trademark) 4015, 4050, 4080, 4300, 4400, or 4800 (both of which are manufactured by BASF), "Ajisper" (registered trademark) PB711 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), or "SOLSPERSE" (registered trademark) 13240, 20000, or 71000 (both of which are manufactured by All of them are manufactured by Lubrizol).

(E) dispersants having a basic group and an acidic group include, for example, "ANTI-TERRA" (registered trademark) -U100 or -204, "DISPERBYK" (registered trademark) -106, -140, - 145, -180, -191, -2001, or -2020, "BYK" (registered trademark) -9076 (manufactured by BYK Chemie Japan), "Ajisper" (registered trademark) PB821 or PB881 (above, All manufactured by Ajinomoto Fine-Techno Co., Ltd.), or "SOLSPERSE" (registered trademark) 9000, 13650, 24000, 33000, 37500, 39000, 56000, or 76500 (all manufactured by Lubrizol) mentioned.

(E) dispersants having only acidic groups include, for example, "DISPERBYK" (registered trademark) -102, -118, -170, or -2096, "BYK" (registered trademark) -P104, or -220S (all manufactured by BYK-Chemie Japan), or "SOLSPERSE" (registered trademark) 3000, 16000, 21000, 36000, or 55000 (all manufactured by Lubrizol).

As the (E) dispersant having neither a basic group nor an acidic group, for example, "DISPERBYK" (registered trademark) -103, -192, -2152, or -2200 (both of which are BYK-Chemie Japan), or "SOLSPERSE" (registered trademark) 27000, 54000, or X300 (all of which are manufactured by Lubrizol).

(E) The amine value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and even more preferably 10 mgKOH/g or more. When the amine value is 5 mgKOH/g or more, the dispersion stability of the (D1) pigment can be improved. On the other hand, the amine value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and even more preferably 100 mgKOH/g or less. When the amine value is 150 mgKOH/g or less, the storage stability of the resin composition can be improved.

The amine value referred to herein is the weight of potassium hydroxide equivalent to the acid reacting with 1 g of the (E) dispersant, and the unit is mgKOH/g. (E) It can be determined by titration with an aqueous potassium hydroxide solution after neutralizing 1 g of the dispersant with an acid. From the value of the amine value, it is possible to calculate the amine equivalent (unit: g/mol), which is the weight of the resin per 1 mol of basic groups such as amino groups. can be calculated.

(E) The acid value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and even more preferably 10 mgKOH/g or more. When the acid value is 5 mgKOH/g or more, the dispersion stability of the pigment (D1) can be improved. On the other hand, the acid value is preferably 200 mgKOH/g or less, more preferably 170 mgKOH/g or less, and even more preferably 150 mgKOH/g or less. When the acid value is 200 mgKOH/g or less, the storage stability of the resin composition can be improved.

The acid value referred to herein is the weight of potassium hydroxide that reacts with 1 g of the (E) dispersant, and the unit is mgKOH/g. (E) It can be determined by titrating 1 g of the dispersant with an aqueous potassium hydroxide solution. From the acid value, the acid equivalent (unit: g/mol), which is the weight of the resin per 1 mol of acidic groups, can be calculated, and (E) the number of acidic groups in the dispersant can be determined.

The (E) dispersant having a polymer chain includes an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, a polyol-based dispersant, a polyethyleneimine-based dispersant, or a polyallylamine. system dispersants. From the viewpoint of pattern processability with an alkaline developer, an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, or a polyol-based dispersant is preferred.

When the negative photosensitive resin composition of the present invention contains a disperse dye as (D1) pigment and/or (D2) dye, the content ratio of (E) dispersant in the negative photosensitive resin composition of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, when the total of (D1) pigment and / or disperse dye and (E) dispersant is 100% by mass. preferable. When the content is 1% by mass or more, the dispersion stability of (D1) the pigment and/or the disperse dye can be improved, and the resolution after development can be improved. On the other hand, the content ratio of (E) the dispersant is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. When the content ratio is 60% by mass or less, the heat resistance of the cured film can be improved.

<(F) polyfunctional thiol compound>
The negative photosensitive resin composition of the present invention preferably further contains a chain transfer agent. A chain transfer agent refers to a compound capable of accepting radicals from the growing end of a polymer chain obtained by radical polymerization during exposure and transferring the radicals to another polymer chain.

The chain transfer agent preferably contains (F) a polyfunctional thiol compound. By containing (F) a polyfunctional thiol compound, the sensitivity during exposure can be improved. It is presumed that this is because the radicals generated by the exposure migrate to other polymer chains, thereby radically cross-linking deep in the film. In particular, for example, when the resin composition contains (Da) a black agent as the (D) colorant described above, the light from exposure is absorbed by the (Da) black agent, so the light does not reach deep into the film. Sometimes. On the other hand, when (F) a polyfunctional thiol compound is contained, radical cross-linking is carried out to the deep part of the film by radical transfer, so sensitivity during exposure can be improved.

In addition, by containing (F) a polyfunctional thiol compound, a cured film having a low taper pattern can be obtained. It is presumed that this is because radical transfer can control the molecular weight of polymer chains obtained by radical polymerization during exposure. That is, containing (F) a polyfunctional thiol compound inhibits the formation of significant high-molecular-weight polymer chains due to excessive radical polymerization during exposure, and suppresses an increase in the softening point of the resulting film. Therefore, it is considered that the reflow property of the pattern during heat curing is improved, and a pattern shape with a low taper can be obtained.

Furthermore, the negative photosensitive resin composition of the present invention contains (C1-1) the specific oxime ester-based photopolymerization initiator and (F) the polyfunctional thiol compound described above, thereby reducing residue generation during development. In addition, it is possible to suppress the change in pattern opening dimension width before and after heat curing. This is presumably because (G) the polyfunctional thiol compound suppresses oxygen inhibition on the film surface, thereby promoting UV curing during exposure. That is, it is considered that (C1-1) UV curing by the specific oxime ester photopolymerization initiator is significantly accelerated. (D) As a colorant, in particular, when (D1) pigment is contained, oxygen inhibition suppression on the film surface causes (D1) pigment to be fixed in the cured portion by crosslinking during UV curing, and (D1) pigment It is possible to suppress the generation of residues after development derived from. In particular, when (D1a-1a) a benzofuranone-based black pigment is contained as the (Da) black agent, development residues derived from the pigment may occur due to the above-described insufficient alkali resistance of the pigment. Even in such a case, inclusion of (G) a polyfunctional thiol compound promotes UV curing by suppressing oxygen inhibition on the film surface, and suppresses the above-mentioned pigment-derived development residue.

Further, as described above, the negative photosensitive resin composition of the present invention has the above-described (B4) from the viewpoint of suppressing changes in pattern opening dimension width before and after heat curing and forming a low tapered pattern after development. It preferably contains an alicyclic group-containing radically polymerizable compound and (F) a polyfunctional thiol compound.

(F) the polyfunctional thiol compound, the compound represented by the general formula (83), the compound represented by the general formula (85), and the compound selected from the group consisting of the compound represented by the general formula (85) It is preferable to contain more than one type.

In general formulas (83) to (85), X ⁴² and X ⁴³ each represent a divalent organic group. X ⁴⁴ and X ⁴⁵ each independently represent a direct bond or an alkylene chain having 1 to 10 carbon atoms. Y ⁴² to Y ⁵³ each independently represent a direct bond, an alkylene chain having 1 to 10 carbon atoms or a group represented by general formula (86). Z ⁴⁰ to Z ⁵¹ each independently represent a direct bond or an alkylene chain having 1 to 10 carbon atoms. R ²³¹ to R ²⁴² each independently represent an alkylene chain having 1 to 10 carbon atoms. R ²⁴³ to R ²⁴⁵ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms. a, b, c, d, e, f, h, i, j, k, w, and x each independently represent 0 or 1; g and l each independently represents an integer of 0 to 10; m, n, o, p, q, r, s, t, u, v, y, and z each independently represents an integer of 0-10. α and β each independently represent an integer of 1-10. In general formulas (83) to (85), X ⁴² and X ⁴³ each independently represent an aliphatic structure having 1 to 10 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms and a A divalent organic group having one or more selected from aromatic structures is preferred. a, b, c, d, e, f, h, i, j, k, w, and x are each independently preferably 1; Each of g and l is preferably an integer of 0 to 5 independently. m, n, o, p, q, r, s, t, u, v, y, and z are each independently preferably 0. α and β are each independently preferably an integer of 1 to 5, more preferably 1 or 2, and even more preferably 1. The alkyl groups, alkylene chains, aliphatic structures, alicyclic structures and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.

In general formula (86), R ²⁴⁶ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. ^Z52 represents a group represented by general formula (87) or a group represented by general formula (88). a represents an integer of 1 to 10, b represents an integer of 1 to 4, c represents 0 or 1, d represents an integer of 1 to 4, e represents 0 or 1 . If c is 0, then d is 1. In general formula (88), R ²⁴⁷ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. In general formula (86), R ²⁴⁶ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. ^Z52 represents a group represented by general formula (87) or a group represented by general formula (88). a represents an integer of 1 to 10, b represents an integer of 1 to 4, c represents 0 or 1, d represents an integer of 1 to 4, e represents 0 or 1 . If c is 0, then d is 1. In general formula (88), R ²⁴⁷ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. In general formula (86), c is preferably 1, and e is preferably 1. In general formula (88), R ²⁴⁷ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a methyl group.

(F) Polyfunctional thiol compounds include, for example, β-mercaptopropionic acid, β-methyl β-mercaptopropionate, 2-ethylhexyl β-mercaptopropionate, stearyl β-mercaptopropionate, β-methoxybutyl β-mercaptopropionate, β -mercaptobutanoic acid, methyl β-mercaptobutanoate, methyl thioglycolate, n-octyl thioglycolate, methoxybutyl thioglycolate, 1,4-bis(3-mercaptobutanoyloxy)butane, 1,4-bis (3-mercaptopropionyloxy)butane, 1,4-bis(thioglycoloyloxy)butane, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercapto propionate), ethylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoethyl) ether , ethylene glycol bis (3-mercaptopropyl) ether, ethylene glycol bis (2-mercaptopropyl) ether, ethylene glycol bis (3-mercaptobutyl) ether, diethylene glycol bis (2-mercaptoethyl) ether, tetraethylene glycol bis (2 -mercaptoethyl) ether, propylene glycol bis(2-mercaptoethyl) ether, butylene glycol bis(2-mercaptoethyl) ether, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3- mercaptopropylthio)ethane, diethylenethioglycol bis(2-mercaptoethyl)ether, tetraethylenethioglycolbis(2-mercaptoethyl)ether, 1,3-bis(2-mercaptoethylthio)propane, 1,4-bis (2-mercaptoethylthio)butane, trimethylolethane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (thioglycolate), 1,3,5-tris [(3-mercaptopropionyloxy) ethyl] isocyanuric acid, 1,3,5-tris [(3- mercaptobutanoyloxy)ethyl]isocyanuric acid, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3- mercaptopropionate) or dipentaerythritol hexakis (3-mercaptobutyrate).

From the viewpoint of improving sensitivity during exposure, forming a pattern with a low taper shape, and suppressing residues after development, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2 -mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(2-mercaptoethyl) ether, ethylene glycol bis(3-mercaptopropyl) ether, ethylene glycol bis(2-mercaptopropyl) ether , ethylene glycol bis (3-mercaptobutyl) ether, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, trimethylol ethane tris (3-mercaptopropio trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (thioglycolate), 1,3,5-tris[(3-mercaptopropionyloxy)ethyl]isocyanuric acid, 1,3,5-tris[(3-mercaptobutanoyloxy)ethyl]isocyanuric acid, pentaerythritol tetrakis(3-mercaptopropio butyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropionate) or dipentaerythritol hexakis (3-mercaptobutyrate) preferable. In addition, from the viewpoint of suppressing residues after development, ethylene glycol bis (2-mercaptoethyl) ether, ethylene glycol bis (3-mercaptopropyl) ether, ethylene glycol bis (2-mercaptopropyl) ether, ethylene glycol bis (3- Mercaptobutyl)ether, 1,2-bis(2-mercaptoethylthio)ethane or 1,2-bis(3-mercaptopropylthio)ethane are more preferred.

The content of the (F) polyfunctional thiol compound in the negative photosensitive resin composition of the present invention is 0 when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. 0.01 parts by mass or more is preferable, 0.1 parts by mass or more is more preferable, 0.3 parts by mass or more is even more preferable, 0.5 parts by mass or more is even more preferable, and 1 part by mass or more is particularly preferable. When the content is 0.01 part by mass or more, the sensitivity during exposure can be improved, and a cured film having a pattern shape with a low taper can be obtained. In addition, generation of residue during development can be suppressed. On the other hand, the content of the polyfunctional thiol compound (F) is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and 5 parts by mass or less. is particularly preferred. When the content is 15 parts by mass or less, a pattern with a low taper shape can be formed, the generation of residue after development can be suppressed, and the heat resistance of the cured film can be improved.

<Sensitizer>
The negative photosensitive resin composition of the present invention preferably further contains a sensitizer. The sensitizer is a compound capable of absorbing energy due to exposure, generating excited triplet electrons by internal conversion and intersystem crossing, and transferring energy to the above-mentioned (C1) photopolymerization initiator or the like. say.

By containing a sensitizer, the sensitivity at the time of exposure can be improved. This is because the sensitizer absorbs long-wavelength light that the (C1) photopolymerization initiator or the like does not absorb, and the energy is transferred from the sensitizer to the (C1) photopolymerization initiator or the like. This is presumed to be because the photoreaction efficiency can be improved.

As the sensitizer, a thioxanthone-based sensitizer is preferred. Examples of thioxanthone-based sensitizers include thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. be done.

The content of the sensitizer in the negative photosensitive resin composition of the present invention is 0.01 parts by mass when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. The above is preferable, 0.1 parts by mass or more is more preferable, 0.5 parts by mass or more is still more preferable, and 1 part by mass or more is particularly preferable. When the content is 0.01 parts by mass or more, the sensitivity during exposure can be improved. On the other hand, the content of the sensitizer is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. When the content is 15 parts by mass or less, the resolution after development can be improved, and a cured film having a low taper pattern can be obtained.

<Polymerization inhibitor>
The negative photosensitive resin composition of the present invention preferably further contains a polymerization inhibitor. The polymerization inhibitor captures the radicals generated during exposure or the radicals at the growing terminal of the polymer chain obtained by radical polymerization during exposure and holds them as stable radicals, thereby terminating radical polymerization. Refers to possible compounds.

By containing an appropriate amount of the polymerization inhibitor, the generation of residue after development can be suppressed, and the resolution after development can be improved. It is presumed that this is because the polymerization inhibitor captures excess radicals generated during exposure or radicals at growing ends of high-molecular-weight polymer chains, thereby suppressing the progress of excessive radical polymerization.

As the polymerization inhibitor, a phenol-based polymerization inhibitor is preferred. Phenolic polymerization inhibitors include, for example, 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 4 -t-butylcatechol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-1,4-hydroquinone, or 2,5-di-t-amyl-1, 4-hydroquinone, or "IRGANOX" (registered trademark) 245, 259, 565, 1010, 1035, 1076, 1098, 1135, 1330, 1425, 1520, 1726, or 3114 (both of which are manufactured by BASF Corporation).

The content of the polymerization inhibitor in the negative photosensitive resin composition of the present invention is 0.01 parts by mass when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. The above is preferable, 0.03 parts by mass or more is more preferable, 0.05 parts by mass or more is still more preferable, and 0.1 parts by mass or more is particularly preferable. When the content is 0.01 part by mass or more, the resolution after development and the heat resistance of the cured film can be improved. On the other hand, the content of the polymerization inhibitor is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. When the content is 10 parts by mass or less, the sensitivity during exposure can be improved.

<Crosslinking agent>
The negative photosensitive resin composition of the present invention preferably further contains a cross-linking agent. A cross-linking agent refers to a compound having a cross-linkable group capable of bonding with a resin. By containing a cross-linking agent, the hardness and chemical resistance of the cured film can be improved. This is presumably because the cross-linking agent can introduce a new cross-linking structure into the cured film of the resin composition, thereby improving the cross-linking density.

In addition, by including a cross-linking agent, it becomes possible to form a pattern with a low taper shape after thermal curing. This is because the (F) cross-linking agent forms a cross-linked structure between the polymers, which inhibits the dense orientation of the polymer chains and maintains the reflowability of the pattern during heat curing, resulting in a pattern with a low taper shape. formation is possible. The cross-linking agent is preferably a compound having two or more thermal cross-linking properties in the molecule, such as an alkoxymethyl group, methylol group, epoxy group, or oxetanyl group.

Compounds having two or more alkoxymethyl groups or methylol groups in the molecule include, for example, DML-PC, DML-OC, DML-PTBP, DML-PCHP, DML-MBPC, DML-MTrisPC, DMOM-PC, DMOM- PTBP, TriML-P, TriML-35XL, TML-HQ, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPHAP, or HMOM-TPHAP (any of the above Honshu Chemical Industry Co., Ltd.), or "NIKALAC" (registered trademark) MX-290, MX-280, MX-270, MX-279, MW-100LM, MW-30HM, MW-390, Alternatively, the same MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.

Compounds having two or more epoxy groups in the molecule include, for example, "Epolite" (registered trademark) 40E, 100E, 400E, 70P, 1500NP, 80MF, 3002, or 4000 (any of these Kyoeisha Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, EX-216L, EX-321L, or EX-850L (all of these are manufactured by Nagase ChemteX Corporation), “jER” (registered Trademark) 828, 1002, 1750, YX8100-BH30, E1256, or E4275 (all manufactured by Mitsubishi Chemical Corporation), GAN, GOT, EPPN-502H, NC-3000, or NC-6000 , all manufactured by Nippon Kayaku), “EPICLON” (registered trademark) EXA-9583, HP4032, N695, or HP7200 (all manufactured by Dainippon Ink and Chemicals), “TECHMORE” (registered trademark) ) VG-3101L (manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark) S, the same G, or the same P (all of these are manufactured by Nissan Chemical Industries, Ltd.), or "Epototo" (registered trademark) YH-434L ( manufactured by Tohto Kasei Co., Ltd.).

Examples of compounds having two or more oxetanyl groups in the molecule include "ETERNACOLL" (registered trademark) EHO, OXBP, OXTP, or OXMA (all of which are manufactured by Ube Industries, Ltd.), or oxetaneated phenol novolak. is mentioned.

The content of the cross-linking agent in the negative photosensitive resin composition of the present invention is 0.5 parts by mass or more when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. is preferred, 1 part by mass or more is more preferred, 2 parts by mass or more is even more preferred, 3 parts by mass or more is even more preferred, and 5 parts by mass or more is particularly preferred. When the content is 0.5 parts by mass or more, the hardness and chemical resistance of the cured film can be improved, and a low tapered pattern can be formed after heat curing. On the other hand, the content of the cross-linking agent is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less. When the content is 50 parts by mass or less, the hardness and chemical resistance of the cured film can be improved, and a low tapered pattern can be formed after heat curing.

<Silane coupling agent>
The negative photosensitive resin composition of the present invention preferably further contains a silane coupling agent. A silane coupling agent refers to a compound having a hydrolyzable silyl group or silanol group. By containing the silane coupling agent, the interaction between the cured film of the resin composition and the underlying substrate increases, and the adhesion to the underlying substrate and the chemical resistance of the cured film can be improved. Preferred silane coupling agents are trifunctional organosilanes, tetrafunctional organosilanes, and silicate compounds.

Trifunctional organosilanes include, for example, methyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, Methoxysilane, 4-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 3-trimethoxysilylpropylsuccinic anhydride, 3,3,3-trifluoropropyltri Methoxysilane, 3-[(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(4-aminophenyl)propyltrimethoxysilane, 1-(3-trimethoxysilane silylpropyl)urea, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,3,5-tris(3 -trimethoxysilylpropyl)isocyanuric acid, or Nt-butyl-2-(3-trimethoxysilylpropyl)succinimide. Examples of tetrafunctional organosilanes or silicate compounds include organosilanes represented by general formula (73).

In general formula (73), R ²²⁶ to R ²²⁹ each independently represent hydrogen, an alkyl group, an acyl group or an aryl group, and x represents an integer of 1-15. In general formula (73), R ²²⁶ to R ²²⁹ are each independently preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. , hydrogen, an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms is more preferable. The alkyl group, acyl group, and aryl group described above may be unsubstituted or substituted.

Examples of the organosilane represented by the general formula (73) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane and the like. functional organosilane, or methyl silicate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M silicate 51, silicate 40, or silicate 45 (all of which are manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51, methyl silicate 53A, ethyl silicate 40, Alternatively, silicate compounds such as Ethyl Silicate 48 (both of which are manufactured by Colcoat Co.) can be used.

The content of the silane coupling agent in the negative photosensitive resin composition of the present invention is 0.01 mass when the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound is 100 parts by mass. Part or more is preferable, 0.1 part by mass or more is more preferable, 0.5 part by mass or more is still more preferable, and 1 part by mass or more is particularly preferable. When the content is 0.01 part by mass or more, the adhesion to the underlying substrate and the chemical resistance of the cured film can be improved. On the other hand, the content of the silane coupling agent is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. The resolution after development can be improved as content is 15 mass parts or less.

<Surfactant>
The negative photosensitive resin composition of the present invention may further contain a surfactant. A surfactant refers to a compound having a hydrophilic structure and a hydrophobic structure. By including an appropriate amount of surfactant, the surface tension of the resin composition can be arbitrarily adjusted, the leveling property during coating can be improved, and the film thickness uniformity of the coating film can be improved. As the surfactant, a fluororesin-based surfactant, a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant is preferable.

The content ratio of the surfactant in the negative photosensitive resin composition of the present invention is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and 0 01% by mass or more is more preferable. When the content ratio is 0.001% by mass or more, the leveling property during coating can be improved. On the other hand, the surfactant content is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.03% by mass or less. When the content ratio is 1% by mass or less, the leveling property during coating can be improved.

<Solvent>
The negative photosensitive resin composition of the present invention preferably further contains a solvent. A solvent is a compound capable of dissolving various resins and various additives contained in the resin composition. By containing a solvent, various resins and various additives to be contained in the resin composition can be uniformly dissolved, and the transmittance of the cured film can be improved. Moreover, the viscosity of the resin composition can be arbitrarily adjusted, and a film can be formed on the substrate with a desired film thickness. In addition, the surface tension of the resin composition or the drying speed during application can be arbitrarily adjusted, and the leveling property during application and the uniformity of the film thickness of the coating film can be improved.

From the viewpoint of solubility of various resins and various additives, the solvent is preferably a compound having an alcoholic hydroxyl group, a compound having a carbonyl group, or a compound having three or more ether bonds. In addition, compounds having a boiling point of 110 to 250° C. under atmospheric pressure are more preferred. By setting the boiling point to 110° C. or higher, the solvent evaporates appropriately during coating and the coating film dries up, so coating unevenness can be suppressed and film thickness uniformity can be improved. On the other hand, by setting the boiling point to 250° C. or lower, the amount of solvent remaining in the coating film can be reduced. Therefore, it is possible to reduce the amount of film shrinkage during heat curing, improve the flatness of the cured film, and improve the film thickness uniformity.

Examples of compounds having an alcoholic hydroxyl group and having a boiling point of 110 to 250° C. under atmospheric pressure include diacetone alcohol, ethyl lactate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and dipropylene glycol. monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, or tetrahydrofurfuryl alcohol.

Compounds having a carbonyl group and having a boiling point of 110 to 250° C. under atmospheric pressure include, for example, 3-methoxy-n-butyl acetate, 3-methyl-3-n-butyl acetate, and propylene glycol monomethyl ether acetate. , dipropylene glycol monomethyl ether acetate, or γ-butyrolactone.

Examples of compounds having three or more ether bonds and having a boiling point of 110 to 250° C. under atmospheric pressure include diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and dipropylene glycol dimethyl ether.

The content ratio of the solvent in the negative photosensitive resin composition of the present invention can be appropriately adjusted according to the coating method and the like. For example, when forming a coating film by spin coating, it is generally 50 to 95% by mass of the total negative photosensitive resin composition.

When disperse dyes are contained as (D1) pigments and/or (D2) dyes as (D) colorants, the solvent is preferably a solvent having a carbonyl group or an ester bond. By containing a solvent having a carbonyl group or an ester bond, it is possible to improve the dispersion stability of the disperse dye as (D1) pigment and/or (D2) dye. Moreover, from the viewpoint of dispersion stability, the solvent is more preferably a solvent having an acetate bond. By containing a solvent having an acetate bond, it is possible to improve the dispersion stability of disperse dyes as (D1) pigments and/or (D2) dyes.

Solvents having an acetate bond include, for example, 3-methoxy-n-butyl acetate, 3-methyl-3-methoxy-n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol. monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, or 1,4-butanediol diacetate.

In the negative photosensitive resin composition of the present invention, the content ratio of the solvent having a carbonyl group or an ester bond in the solvent is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 70 to 100% by mass. % is more preferred. When the content ratio is 30 to 100% by mass, the dispersion stability of the (D1) pigment can be improved.

<Other additives>
The negative photosensitive resin composition of the present invention may further contain other resins or precursors thereof. Other resins or precursors thereof include, for example, polyamides, polyamideimides, epoxy resins, novolak resins, urea resins, or polyurethanes, or precursors thereof.

<Method for producing the negative photosensitive resin composition of the present invention>
A representative method for producing the negative photosensitive resin composition of the present invention will be described. (D) When containing (D1) a pigment containing (Da) a black agent as a colorant, (E) a dispersant is added to a solution of (A1) the first resin and (A2) the second resin, and a disperser is used to disperse the (D1) pigment in this mixed solution to prepare a pigment dispersion. Next, (B) a radically polymerizable compound, (C1) a photopolymerization initiator, other additives, and an optional solvent are added to this pigment dispersion, and stirred for 20 minutes to 3 hours to form a uniform solution. . After stirring, the resulting solution is filtered to obtain the negative photosensitive resin composition of the present invention.

Dispersers include, for example, ball mills, bead mills, sand grinders, three roll mills, or high speed impact mills. A bead mill is preferable from the viewpoint of dispersion efficiency and fine dispersion. Bead mills include, for example, coball mills, basket mills, pin mills, or dyno mills. Bead mill beads include, for example, titania beads, zirconia beads, or zircon beads. The bead diameter of the bead mill is preferably 0.01 to 6 mm, more preferably 0.015 to 5 mm, even more preferably 0.03 to 3 mm. (D1) When the primary particle size of the pigment and the particle size of the secondary particles formed by aggregation of the primary particles are several hundred nm or less, fine beads of 0.015 to 0.1 mm are preferable. In this case, a bead mill equipped with a centrifugal separator capable of separating fine beads and a pigment dispersion is preferred. On the other hand, when the (D1) pigment contains coarse particles of several hundred nanometers or more, beads of 0.1 to 6 mm are preferred from the viewpoint of improving dispersion efficiency.

<Hardening pattern of low taper pattern shape>
The negative photosensitive resin composition of the present invention can provide a cured film containing a cured pattern with a low taper pattern shape. The taper angle of the inclined side in the cross section of the cured pattern included in the cured film obtained from the negative photosensitive resin composition of the present invention is preferably 1° or more, more preferably 5° or more, and further preferably 10° or more. 12° or more is even more preferred, and 15° or more is particularly preferred. When the taper angle is 1° or more, the light emitting elements can be integrated and arranged at high density, thereby improving the resolution of the display device. On the other hand, the taper angle of the inclined side in the cross section of the cured pattern included in the cured film is preferably 60 ° or less, more preferably 55 ° or less, even more preferably 50 ° or less, even more preferably 45 ° or less, and 40 ° or less. Especially preferred. If the taper angle is 60° or less, it is possible to prevent disconnection when forming electrodes such as a transparent electrode or a reflective electrode. In addition, since electric field concentration at the edge portion of the electrode can be suppressed, deterioration of the light emitting element can be suppressed.

<Curing pattern having stepped shape>
The negative photosensitive resin composition of the present invention has a stepped shape with a sufficient film thickness difference between the thick film portion and the thin film portion while maintaining high sensitivity, and has a cured pattern with a low taper pattern shape. can be formed. In addition, it is possible to reduce the taper by controlling the pattern shape after development, and it is possible to suppress the change in the pattern opening dimension width before and after heat curing, so the step shape and pattern opening dimension formed after development can be maintained after heat curing. Therefore, the negative-type photosensitive resin composition of the present invention is particularly suitable for collectively forming the stepped shape of the pixel dividing layer in the organic EL display. Similarly, electrode insulating layer, wiring insulating layer, interlayer insulating layer, TFT flattening layer, electrode flattening layer, wiring flattening layer, TFT protective layer, electrode protective layer, wiring protective layer, gate insulating layer, color filter, black It is suitable for collectively forming stepped shapes of matrix or black column spacers.

FIG. 3 shows an example of a cross-section of a stepped cured pattern obtained from the negative photosensitive resin composition of the present invention. The thick film portion 34 in the stepped shape corresponds to the cured portion at the time of exposure, and has the maximum film thickness of the cured pattern. The thin film portions 35a, 35b, and 35c in the stepped shape correspond to halftone exposure portions during exposure, and have a film thickness smaller than that of the thick film portion 34. FIG. The taper angles θ _a , θ _b , θ _c , θ _d , and θ _e of the inclined sides 36 a , 36 b , 36 c , 36 d , and 36 e in the cross section of the curing pattern having a step shape are preferably low tapers. .

The taper angles θ _a , θ _b , θ _c , θ _d , and θ _e referred to herein are, as shown in FIG. A curing pattern having a stepped shape formed by a horizontal side of 35c and inclined sides 36a, 36b, 36c, 36d, and 36e in the cross section of the curing pattern having a stepped shape that intersects the horizontal sides of thin film portions 35a, 35b, and 35c. A corner inside a cross section. Here, forward taper means that the taper angle is within a range of greater than 0° and less than 90°, and reverse taper means that the taper angle is within a range of greater than 90° and less than 180°. . Further, the term "rectangle" means that the taper angle is 90°, and the term "low taper" means that the taper angle is greater than 0° and within the range of 60°.

In the thickness between the plane of the lower surface and the plane of the upper surface of the cured pattern having a stepped shape obtained from the negative photosensitive resin composition of the present invention, the thick film portion 34 is the region having the largest thickness, A region having a thickness smaller than that of the thick film portion 34 is referred to as a thin film portion 35 . When the film thickness of the thick film portion 34 is (T _FT ) μm, and the film thickness of the thin film portions 35a, 35b, and 35c arranged in the thick film portion 34 via at least one step shape is (T _HT ) μm. , The film thickness difference (ΔT _FT-HT ) μm between (T _FT ) and (T _HT ) is preferably 0.5 μm or more, more preferably 1.0 μm or more, further preferably 1.5 μm or more, and 2.0 μm. The above is even more preferable, 2.5 μm or more is particularly preferable, and 3.0 μm or more is most preferable. When the film thickness difference is within the range described above, the contact area with the vapor deposition mask when forming the light emitting layer can be reduced, so that it is possible to suppress the decrease in the yield of the panel due to the generation of particles, and to suppress the deterioration of the light emitting element. can be done. In addition, since a single cured pattern having a stepped shape has a sufficient film thickness difference, the process time can be shortened. On the other hand, the film thickness difference (ΔT _FT-HT ) μm is preferably 10.0 μm or less, more preferably 9.5 μm or less, even more preferably 9.0 μm or less, even more preferably 8.5 μm or less, and 8.0 μm or less. is particularly preferred. When the film thickness difference is within the range described above, it is possible to reduce the exposure amount when forming a cured pattern having a stepped shape, thereby shortening the tact time.

The film thickness (T _FT ) μm of the thick film portion 34 and the film thickness (T _HT ) μm of the thin film portions 35a, 35b, and 35c preferably satisfy the relationships represented by general formulas (α) to (γ).
2.0≦(T _FT )≦10.0 (α)
0.20≦( _THT )≦7.5 (β)
0.10×(T _FT )≦(T _HT )≦0.75×(T _FT ) (γ)

It is preferable that the film thickness (T _FT ) μm of the thick film portion 34 and the film thickness (T _HT ) μm of the thin film portions 35a, 35b, and 35c further satisfy the relationships represented by the general formulas (δ) to (ζ). .
2.0≦(T _FT )≦10.0 (δ)
0.30≦( _THT )≦7.0 (ε)
0.15×(T _FT )≦(T _HT )≦0.70×(T _FT ) (ζ)

When the film thickness (T _FT ) μm of the thick film portion 34 and the film thickness (T _HT ) μm of the thin film portions 35a, 35b, and 35c are within the ranges described above, deterioration of the light emitting element can be suppressed, and process Time can be shortened.

In the organic EL display of the present invention, the taper angle of the inclined side in the cross section of the stepped cured pattern obtained from the negative photosensitive resin composition is preferably 1° or more, more preferably 5° or more, and 10°. 12° or more is more preferable, and 15° or more is particularly preferable. When the taper angle is within the range described above, the light emitting elements can be integrated and arranged at high density, thereby improving the resolution of the organic EL display. On the other hand, the taper angle of the inclined side in the cross section of the cured pattern is preferably 60° or less, more preferably 55° or less, even more preferably 50° or less, even more preferably 45° or less, and particularly preferably 40° or less. When the taper angle is within the range described above, it is possible to prevent disconnection when forming electrodes such as a transparent electrode or a reflective electrode. In addition, since electric field concentration at the edge portion of the electrode can be suppressed, deterioration of the light emitting element can be suppressed.

<Manufacturing process of organic EL display>
As a process using the negative photosensitive resin composition of the present invention, a schematic cross-sectional view is shown in FIG. to explain. First, (step 1) a thin film transistor (hereinafter referred to as "TFT") 2 is formed on a glass substrate 1, a film of a photosensitive material for a TFT flattening film is formed, patterned by photolithography, and then thermally cured. to form a cured film 3 for flattening the TFT. Next, (step 2) a film of silver-palladium-copper alloy (hereinafter referred to as "APC") is formed by sputtering, patterned by etching using a photoresist to form an APC layer, and furthermore, an upper layer of the APC layer. A film of indium tin oxide (hereinafter referred to as "ITO") is formed by sputtering, patterned by etching using a photoresist, and a reflective electrode 4 is formed as a first electrode. Thereafter, (step 3) the negative photosensitive resin composition of the present invention is applied and prebaked to form a prebaked film 5a. Next, (Step 4), actinic rays 7 are irradiated through a mask 6 having a desired pattern. Next, (step 5) after development and pattern processing, bleaching exposure and middle baking are performed as necessary, and heat curing is performed to form a cured pattern 5b having a desired pattern as a light-shielding pixel dividing layer. Form. Thereafter, (step 6) an EL light-emitting layer 8 is formed by vapor deposition of an EL light-emitting material through a mask, a film of a magnesium-silver alloy (hereinafter referred to as "MgAg") is formed by vapor deposition, and a photoresist is formed. A transparent electrode 9 is formed as a second electrode by patterning by etching. Next (step 7), a film of a photosensitive material for flattening film is formed, patterned by photolithography, thermally cured to form a cured film 10 for flattening, and then a cover glass 11 is bonded. Thus, an organic EL display having the negative photosensitive resin composition of the present invention as a light-shielding pixel dividing layer is obtained.

<Manufacturing process of liquid crystal display>
As another process using the negative photosensitive resin composition of the present invention, a cured film of the composition is formed into a black column spacer (hereinafter, "BCS") of a liquid crystal display and a black matrix (hereinafter, "BM") of a color filter. ) will be described with reference to a schematic cross-sectional view of FIG.

As shown in FIG. 2, first, (step 1) a backlight unit (hereinafter referred to as "BLU") 13 is formed on a glass substrate 12 to obtain a glass substrate 14 having a BLU.

Further, (Step 2) TFTs 16 are formed on another glass substrate 15, a film of a photosensitive material for TFT flattening film is formed, patterned by photolithography, and then thermally cured to form a TFT flattening film. A cured film 17 is formed. Next, (step 3) an ITO film is formed by sputtering, patterned by etching using a photoresist, a transparent electrode 18 is formed, and a flattening film 19 and an alignment film 20 are formed thereon. Thereafter, (step 4) the negative photosensitive resin composition of the present invention is applied and prebaked to form a prebaked film 21a. Next, (step 5), actinic actinic rays 23 are irradiated through a mask 22 having a desired pattern. Next, (step 6) after development and pattern processing, bleaching exposure and middle baking are performed as necessary, and heat curing is performed to form a cured pattern 21b having a desired pattern as a light-shielding BCS, A glass substrate 24 with BCS is obtained. Next, (step 7) the glass substrate 14 and the glass substrate 24 are bonded together to obtain a glass substrate 25 having BLU and BCS.

Further, (Step 8) three color filters 27 of red, green and blue are formed on another glass substrate 26 . Next, (step 9) a cured pattern 28 having a desired pattern as a light-shielding BM is formed from the negative photosensitive resin composition of the present invention in the same manner as described above. Thereafter, (step 10) a film of a photosensitive material for planarization is formed, patterned by photolithography, and thermally cured to form a cured film 29 for planarization, and an alignment film 30 is formed thereon. Thus, the color filter substrate 31 is obtained. Next, (step 11) the glass substrate 25 having the BLU and BCS and the color filter substrate 31 are bonded together (step 12) to obtain the glass substrate 32 having the BLU, BCS and BM. Next, (Step 13) liquid crystal is injected to form a liquid crystal layer 33, thereby obtaining a liquid crystal display having the negative photosensitive resin composition of the present invention as BCS and BM.

As described above, according to the method for manufacturing an organic EL display and a liquid crystal display using the negative photosensitive resin composition of the present invention, the patterned, polyimide and/or polybenzoxazole-containing, highly heat-resistant Moreover, since it is possible to obtain a light-shielding cured film, it leads to an improvement in yield, performance, and reliability in the production of organic EL displays and liquid crystal displays.

According to the process using the negative photosensitive resin composition of the present invention, since the resin composition is photosensitive, it can be patterned directly by photolithography. Therefore, compared with a process using a photoresist, the number of steps can be reduced, so that the productivity of organic EL displays and liquid crystal displays can be improved, and the process time and takt time can be shortened.

<Display device using a cured film obtained from the negative photosensitive resin composition of the present invention>
A cured film obtained from the negative photosensitive resin composition of the present invention can suitably constitute an organic EL display or a liquid crystal display.

Moreover, the negative photosensitive resin composition of the present invention can obtain a pattern shape with a low taper and can obtain a cured film excellent in high heat resistance. Therefore, it is suitable for applications requiring high heat resistance and a low taper pattern shape, such as an insulating layer such as a pixel dividing layer of an organic EL display, a TFT flattening layer, or a TFT protective layer. In particular, in applications where problems due to heat resistance and pattern shape are assumed, such as element defects or characteristic deterioration due to degassing due to thermal decomposition, and disconnection of electrode wiring due to highly tapered pattern shape, the negative of the present invention can be used. By using the cured film of the type photosensitive resin composition, it is possible to manufacture a highly reliable device free from the above-described problems. Furthermore, since the cured film has excellent light-shielding properties, it is possible to prevent the electrode wiring from becoming visible or to reduce the reflection of external light, thereby improving the contrast in image display. Therefore, by using the cured film obtained from the negative photosensitive resin composition of the present invention as a pixel dividing layer, a TFT flattening layer, or a TFT protective layer of an organic EL display, polarized light can be obtained on the light extraction side of the light emitting element. Contrast can be improved without forming plates and quarter-wave plates.

Also, the organic EL display of the present invention preferably has a curved display portion. The radius of curvature of the curved surface is preferably 0.1 mm or more, and more preferably 0.3 mm or more, from the viewpoint of suppressing defective display caused by disconnection or the like in the display portion formed of the curved surface. In addition, the radius of curvature of the curved surface is preferably 10 mm or less, more preferably 7 mm or less, and even more preferably 5 mm or less, from the viewpoint of miniaturization and high resolution of the organic EL display.

A method for manufacturing a display device using the negative photosensitive resin composition of the present invention has the following steps (1) to (4).
(1) forming a coating film of the negative photosensitive resin composition of the present invention on a substrate;
(2) a step of irradiating the coating film of the negative photosensitive resin composition with actinic radiation through a photomask;
(3) developing with an alkaline solution to form a pattern of the negative photosensitive resin composition;
(4) A step of heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.

<Step of forming a coating film>
A method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes (1) forming a coating film of the negative photosensitive resin composition on a substrate. As a method for forming a film of the negative photosensitive resin composition of the present invention, for example, a method of applying the above-described resin composition on a substrate, or a method of applying the above-described resin composition on a substrate in a pattern. method.

As a substrate, for example, an oxide or metal (molybdenum, silver, copper, aluminum, chromium, or titanium) having one or more selected from indium, tin, zinc, aluminum, and gallium is used as an electrode or wiring on glass. etc.), or a substrate on which CNTs (Carbon Nano Tubes) are formed. Examples of oxides containing one or more selected from indium, tin, zinc, aluminum, and gallium include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), and indium gallium zinc oxide. (IGZO), or zinc oxide (ZnO).

<Method of applying the negative photosensitive resin composition of the present invention onto a substrate>
Examples of methods for applying the negative photosensitive resin composition of the present invention onto a substrate include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating. The coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the resin composition, etc., but the coating is normally applied so that the film thickness after coating and prebaking is 0.1 to 30 μm.

After coating the negative photosensitive resin composition of the present invention on a substrate, it is preferable to pre-bake to form a film. An oven, a hot plate, an infrared ray, a flash annealing device, a laser annealing device, or the like can be used for prebaking. A pre-baking temperature of 50 to 150° C. is preferable. The prebake time is preferably 30 seconds to several hours. Two or more stages of pre-baking may be performed, such as pre-baking at 80° C. for 2 minutes and then pre-baking at 120° C. for 2 minutes.

<Method of applying the negative photosensitive resin composition of the present invention in a pattern on a substrate>
Examples of methods for applying the negative photosensitive resin composition of the present invention onto a substrate in a pattern include letterpress printing, intaglio printing, stencil printing, lithographic printing, screen printing, inkjet printing, offset printing, or laser printing. is mentioned. The coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the negative photosensitive resin composition of the present invention, etc., but it is usually applied so that the film thickness after coating and prebaking is 0.1 to 30 μm. .

It is preferable to form a film by applying the negative photosensitive resin composition of the present invention in a pattern on a substrate and then pre-baking it. An oven, a hot plate, an infrared ray, a flash annealing device, a laser annealing device, or the like can be used for prebaking. A pre-baking temperature of 50 to 150° C. is preferable. The prebake time is preferably 30 seconds to several hours. Two or more stages of pre-baking may be performed, such as pre-baking at 80° C. for 2 minutes and then pre-baking at 120° C. for 2 minutes.

<Method of patterning a coating film formed on a substrate>
Examples of the method of patterning the coating film of the negative photosensitive resin composition of the present invention formed on a substrate include a method of direct patterning by photolithography and a method of patterning by etching. From the viewpoint of improving productivity by reducing the number of steps and shortening the process time, a method of directly patterning by photolithography is preferable.

<Step of irradiating actinic radiation through a photomask>
The method for producing a display device using the negative photosensitive resin composition of the present invention comprises (2) a step of irradiating the coating film of the negative photosensitive resin composition described above with actinic rays through a photomask; have After coating and pre-baking the negative photosensitive resin composition of the present invention on a substrate to form a film, an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA) is used. expose. Actinic rays irradiated during exposure include, for example, ultraviolet rays, visible rays, electron beams, X-rays, KrF (wavelength: 248 nm) lasers, ArF (wavelength: 193 nm) lasers, and the like. It is preferable to use j-line (wavelength: 313 nm), i-line (wavelength: 365 nm), h-line (wavelength: 405 nm), or g-line (wavelength: 436 nm) of a mercury lamp. The exposure amount is usually about 100 to 40,000 J/m ² (10 to 4,000 mJ/cm ² ) (i-line illuminometer value), and exposure is performed through a photomask having a desired pattern as necessary. can do.

After exposure, post-exposure baking may be performed. By performing post-exposure baking, effects such as improvement in resolution after development and an increase in the allowable range of development conditions can be expected. Post-exposure baking can use an oven, a hot plate, an infrared ray, a flash annealing device, a laser annealing device, or the like. The post-exposure bake temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure bake time is preferably 10 seconds to several hours. When the post-exposure bake time is 10 seconds to several hours, the reaction proceeds favorably and the development time can sometimes be shortened.

In the method for manufacturing a display device using the negative photosensitive resin composition of the present invention, it is preferable to use a halftone photomask as the photomask. A halftone photomask is a photomask having a pattern including a light-transmitting portion and a light-shielding portion. A photomask having a semi-transparent portion that is higher than the value of the light-shielding portion. By exposing using a halftone photomask, it is possible to form a pattern having a stepped shape after development and heat curing. The cured portion irradiated with actinic rays through the translucent portion corresponds to the thick film portion, and the halftone exposed portion irradiated with actinic rays through the semi-transparent portion corresponds to the thin film portion. corresponds to

In the method of manufacturing a display device using the negative photosensitive resin composition of the present invention, the halftone photomask has a portion where the translucent portion and the semi-translucent portion are adjacent to each other. Since the light-transmitting portion and the semi-light-transmitting portion have adjacent portions, the thick-film portion corresponding to the light-transmitting portion on the photomask and the semi-light-transmitting portion on the photomask after development correspond to the light-transmitting portion. It is possible to form a pattern having the thin film portion and the thin film portion. Further, the halftone photomask has a portion where the light shielding portion and the semitransparent portion are adjacent to each other. After development, a pattern can be formed which has openings corresponding to the light-shielding portions on the photomask and the thin film portions corresponding to the semi-light-transmitting portions on the photomask. Since the halftone photomask has the above portions, it is possible to form a stepped pattern including the thick film portion, the thin film portion, and the opening after development.

As a halftone photomask, when the transmittance of the light-transmitting portion is (% T _FT )%, the transmittance (% T _HT )% of the semi-light-transmitting portion is 10% or more of (% T _FT ). is preferred, 15% or more is more preferred, 20% or more is even more preferred, and 25% or more is particularly preferred. When the transmittance (% T _HT ) % of the semi-transparent portion is within the above range, the exposure amount can be reduced when forming a cured pattern having a stepped shape, thereby shortening the tact time. On the other hand, the transmittance (% T _HT )% of the translucent portion is preferably 60% or less of (% T _FT ), more preferably 55% or less, even more preferably 50% or less, and particularly preferably 45% or less. When the transmittance (% T _HT )% of the semi-transparent portion is within the above range, the film thickness difference between the thick film portion and the thin film portion and the film thickness difference between the thin film portions adjacent to each other on both sides of an arbitrary step are sufficient. can be made large, deterioration of the light-emitting element can be suppressed. In addition, since a single cured pattern having a stepped shape has a sufficient film thickness difference, the process time can be shortened.

Transmittance (% T _HT )% of the semi-transparent portion is 30% of (% T _FT ) in the cured pattern having a stepped shape obtained by irradiating actinic rays through a halftone photomask. The thickness of the thin film portion in the case of (T _HT30 ) μm, and the thickness of the thin film portion in the case where the transmittance (% T _HT )% of the semi-transparent portion is 20% of (% _TFT ) is ( When T _HT20 ) μm, the film thickness difference (ΔT _{HT30 −HT20} ) μm between (T HT30 ) and (T _HT20 ) is preferably 0.3 μm or more, more preferably 0.5 μm or more, and 0.7 μm or more. is more preferable, and 0.8 μm or more is particularly preferable. When the film thickness difference is within the above range, the film thickness difference between the thick film portion and the thin film portion and the film thickness difference between the thin film portions adjacent to each other on both sides of an arbitrary step can be made sufficiently large, thereby preventing deterioration of the light emitting element. can be suppressed. In addition, since a single cured pattern having a stepped shape has a sufficient film thickness difference, the process time can be shortened. On the other hand, the film thickness difference (ΔT _HT30−HT20 ) μm is preferably 1.5 μm or less, more preferably 1.4 μm or less, still more preferably 1.3 μm or less, and particularly preferably 1.2 μm or less. When the film thickness difference is within the above range, it is possible to reduce the occurrence of film thickness variations due to slight fluctuations in the amount of exposure caused by equipment, etc., and thereby improve the film thickness uniformity and the yield in the production of organic EL displays. .

<Step of developing with an alkaline solution to form a pattern>
A method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes (3) a step of developing with an alkaline solution to form a pattern of the negative photosensitive resin composition described above. . After exposure, the film is developed using an automatic developing device or the like. Since the negative type photosensitive resin composition of the present invention has negative type photosensitivity, the unexposed portion is removed with a developer after development, and a relief pattern can be obtained.

As the developer, an alkaline developer is generally used. As the alkaline developer, for example, an organic alkaline solution or an aqueous solution of an alkaline compound is preferable, and from the environmental point of view, an aqueous solution of an alkaline compound, that is, an alkaline aqueous solution is more preferable.

Examples of organic alkaline solutions or compounds exhibiting alkalinity include 2-aminoethanol, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, diethanolamine, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, and acetic acid. (2-dimethylamino)ethyl, (2-dimethylamino)ethyl (meth)acrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide , magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, or potassium carbonate, but from the viewpoint of reducing metal impurities in the cured film and suppressing display defects of the display device, tetramethylammonium hydroxide or tetraethyl hydroxide Ammonium is preferred. An organic solvent may be used as the developer. As the developer, a mixed solution containing both an organic solvent and a poor solvent for the negative photosensitive resin composition of the present invention may be used.

Examples of the developing method include puddle development, spray development, and dip development. Puddle development includes, for example, a method in which the above-described developer is applied to the exposed film as it is and then left for an arbitrary period of time, or a method in which the above-described developer is applied to the exposed film for an arbitrary amount of time in the form of a mist. A method of leaving for an arbitrary time after application by irradiation may be mentioned. Spray development includes a method in which the above-described developer is sprayed onto the film after exposure and is kept in contact with the film for an arbitrary period of time. Dip development includes a method of immersing the film after exposure in the above-described developer for an arbitrary period of time, or a method of immersing the film after exposure in the above-mentioned developer and then continuously irradiating ultrasonic waves for an arbitrary period of time. mentioned. Puddle development is preferable as the development method from the viewpoint of suppressing contamination of the apparatus during development and reducing process costs by reducing the amount of developer used. By suppressing contamination of the device during development, contamination of the substrate during development can be suppressed, and defective display of the display device can be suppressed. On the other hand, from the viewpoint of suppressing the generation of residues after development, spray development is preferred as the development method. Dip development is preferable as the developing method from the viewpoint of reducing the amount of developer used and process costs by reusing the developer.

The development time is preferably 5 seconds or longer, more preferably 10 seconds or longer, still more preferably 30 seconds or longer, and particularly preferably 1 minute or longer. When the development time is within the range described above, it is possible to suppress the generation of residues during alkali development. On the other hand, from the viewpoint of shortening the tact time, the development time is preferably 30 minutes or less, more preferably 15 minutes or less, even more preferably 10 minutes or less, and particularly preferably 5 minutes or less.

After development, the relief pattern obtained is preferably washed with a rinse. As the rinse liquid, water is preferable when an alkaline aqueous solution is used as the developer. As the rinse solution, for example, an aqueous solution of an alcohol such as ethanol or isopropyl alcohol, an aqueous solution of an ester such as propylene glycol monomethyl ether acetate, or an aqueous solution of an acidic compound such as carbon dioxide, hydrochloric acid, or acetic acid may be used. I do not care. An organic solvent may be used as the rinse.

<Step of photocuring the pattern>
In the method for manufacturing a display device using the negative photosensitive resin composition of the present invention, after the step (3) of developing with an alkaline solution to form a pattern of the negative photosensitive resin composition, Furthermore, it is preferable to have a step of photocuring the pattern of the negative photosensitive resin composition.

The step of photocuring the pattern improves the cross-linking density of the pattern and reduces the amount of low-molecular-weight components that cause degassing, thereby improving the reliability of the light-emitting device having the pattern of the negative photosensitive resin composition. can. In addition, when the pattern of the negative photosensitive resin composition has a stepped shape, pattern reflow during heat curing of the pattern can be suppressed, and a sufficient film thickness difference is maintained between the thick film portion and the thin film portion even after heat curing. It is possible to form a pattern having a certain stepped shape. In addition, by maintaining the reflowability of the film surface during heat curing, the flatness is improved, and a decrease in panel yield can be suppressed. Furthermore, in the manufacture of an organic EL display having a pattern of a negative photosensitive resin composition, it is possible to reduce the contact area with the vapor deposition mask when forming the organic EL layer, thereby suppressing the decrease in panel yield due to particle generation. , the deterioration of the light emitting element can be suppressed.

As the step of photocuring the pattern, it is preferable to irradiate the pattern of the negative photosensitive resin composition with an actinic ray. Examples of the method of irradiating with actinic rays include bleaching exposure using an exposure machine such as a stepper, scanner, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA). Lamps used for irradiation with actinic rays in the step of photocuring the pattern include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, Xe excimer lamps, KrF excimer lamps, and ArF excimer lamps. etc.

Examples of actinic rays in the step of photocuring the pattern include ultraviolet rays, visible rays, electron beams, X-rays, XeF (wavelength 351 nm) laser, XeCl (wavelength 308 nm) laser, KrF (wavelength 248 nm) laser, or ArF. (Wavelength 193 nm) laser and the like. From the viewpoint of suppressing pattern reflow during heat curing of the pattern, improving the step thickness, and suppressing the yield reduction of the panel, j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) of mercury lamp, or A g-line (wavelength 436 nm) or a mixed line of i-line, h-line and g-line is preferred.

In the step of photocuring the pattern, the exposure amount of actinic rays is preferably 100 J/m ² (10 mJ/cm ² ) or more in terms of i-line illuminance. On the other hand, the exposure amount of actinic rays is preferably 50,000 J/m ² (5,000 mJ/cm ² ) or less in terms of i-line illuminance. When the exposure dose is within the above range, pattern reflow during heat curing of the pattern of the negative photosensitive resin composition can be suppressed. In addition, it is possible to suppress a decrease in panel yield.

(2) When the photomask in the step of irradiating the coating film of the negative photosensitive resin composition with actinic radiation through a photomask is a halftone photomask, in the step of photocuring the pattern, the activation Let the exposure dose of actinic rays be (E _BLEACH ) mJ/cm ² , and in the step (2) of irradiating actinic rays through the photomask, the exposure dose in the transmissive portion of the photomask be (E _EXPO ) mJ/cm. When ² , the exposure ratio (E _BLEACH )/(E _EXPO ) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and even more preferably 0.7 or more. , 1 or more are particularly preferred. When the exposure dose ratio is within the above range, pattern reflow during thermal curing of the pattern of the negative photosensitive resin composition can be suppressed. In addition, it is possible to suppress a decrease in panel yield. From the viewpoint of improving the step thickness, the exposure amount ratio is preferably 0.5 or more, more preferably 0.7 or more, and even more preferably 1 or more. From the viewpoint of yield improvement, the exposure dose ratio is preferably less than 4, more preferably less than 3.5, and even more preferably less than 3.

Middle baking may be performed after obtaining the pattern of the negative photosensitive resin composition of the present invention. By performing middle baking, the resolution after heat curing is improved, and the pattern shape after heat curing can be arbitrarily controlled. An oven, a hot plate, an infrared ray, a flash annealing device, a laser annealing device, or the like can be used for middle baking. The middle bake temperature is preferably 50 to 250°C, more preferably 70 to 220°C. The middle bake time is preferably 10 seconds to several hours. After middle baking at 100° C. for 5 minutes, middle baking may be performed in two or more stages, such as middle baking at 150° C. for 5 minutes.

<Step of heating the pattern to obtain a cured pattern>
The method for producing a display device using the negative photosensitive resin composition of the present invention includes (4) heating the pattern of the above-described negative photosensitive resin composition to obtain the above-described negative photosensitive resin composition. obtaining a cured pattern. An oven, a hot plate, an infrared ray, a flash annealing apparatus, a laser annealing apparatus, or the like can be used to heat the pattern of the negative photosensitive resin composition of the present invention formed on the substrate. By heating and thermally curing the pattern of the negative photosensitive resin composition of the present invention, the heat resistance of the cured film can be improved, and a low taper pattern shape can be obtained.

The temperature for thermosetting is preferably 150° C. or higher, more preferably 200° C. or higher, and even more preferably 250° C. or higher. When the thermosetting temperature is 150° C. or higher, the heat resistance of the cured film can be improved, and the pattern shape after thermosetting can be further tapered. On the other hand, from the viewpoint of shortening the tact time, the thermosetting temperature is preferably 500° C. or lower, more preferably 450° C. or lower, and even more preferably 400° C. or lower.

The heat curing time is preferably 1 minute or longer, more preferably 5 minutes or longer, still more preferably 10 minutes or longer, and particularly preferably 30 minutes or longer. When the heat curing time is 1 minute or more, the pattern shape after heat curing can be further tapered. On the other hand, from the viewpoint of shortening the tact time, the heat curing time is preferably 300 minutes or less, more preferably 250 minutes or less, even more preferably 200 minutes or less, and particularly preferably 150 minutes or less. Further, the heat curing may be carried out in two or more steps such as heat curing at 150° C. for 30 minutes and then heat curing at 250° C. for 30 minutes.

Further, according to the negative photosensitive resin composition of the present invention, a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, and a TFT protective layer are provided. , an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, a black matrix, or a cured film that can be suitably used for applications such as a black column spacer. In addition, it becomes possible to obtain an element and a display device provided with those cured films. In the organic EL display of the present invention, the cured film is a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, a TFT protective layer, and an electrode protective layer. , a wiring protective layer, a gate insulating layer, a color filter, a black matrix, and a black column spacer. In particular, since the negative photosensitive resin composition of the present invention is excellent in light-shielding properties, it can be used as a light-shielding pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarizing layer, an electrode planarizing layer, and a wiring. It is preferable as a planarizing layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, or a gate insulating layer, and more preferable as a light-shielding pixel dividing layer, an interlayer insulating layer, a TFT planarizing layer, or a TFT protective layer.

Furthermore, according to the method for manufacturing a display device using the negative photosensitive resin composition of the present invention, a highly heat-resistant and light-shielding cured film containing polyimide and/or polybenzoxazole is patterned. Since it is possible to obtain it, it leads to yield improvement, performance improvement and reliability improvement in the production of organic EL displays and liquid crystal displays. In addition, since the negative photosensitive resin composition of the present invention can be directly patterned by photolithography, it is possible to reduce the number of steps compared to a process using a photoresist, which improves productivity. improvement, process time shortening, and takt time shortening are possible.

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to these scopes. The names of the compounds using abbreviations among the compounds used are shown below.
6FDA: 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4′-hexafluoropropane-2,2-diyl-bis(1,2-phthalic anhydride)
A-BPEF: “NK ESTER” (registered trademark) A-BPEF (manufactured by Shin-Nakamura Chemical Co., Ltd.; 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene)
A-DCP: "NK ESTER" (registered trademark) A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.; dimethylol-tricyclodecane diacrylate)
A-DPH-6E: “NK ESTER” (registered trademark) A-DPH-6E (manufactured by Shin-Nakamura Chemical Co., Ltd.; ethoxylated dipentaerythritol hexaacrylate having six oxyethylene structures in the molecule)
APC: Argentum-Palladium-Cupper (silver-palladium-copper alloy)
BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BFE: 1,2-bis(4-formylphenyl)ethane BGPF: 9,9-bis(4-glycidoxyphenyl)fluorene BHPF: 9,9-bis (4-hydroxyphenyl) fluorene Bis-A-AF: 2,2-bis (4-aminophenyl) hexafluoropropane Bk-A1103: "CHROMOFINE" (registered trademark) BLACK A1103 (Dainichisei Kakogyo Co., Ltd.; azo black pigment with a primary particle size of 50 to 100 nm)
Bk-S0084: “PALIOGEN” (registered trademark) BLACK S0084 (manufactured by BASF; perylene-based black pigment with a primary particle size of 50 to 100 nm)
Bk-S0100CF: “IRGAPHOR” (registered trademark) BLACK S0100CF (manufactured by BASF; benzofuranone-based black pigment with a primary particle size of 40 to 80 nm)
cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilaneD. BYK-167: “DISPERBYK” (registered trademark)-167 (manufactured by BYK-Chemie Japan; polyurethane-based dispersant having a tertiary amino group with an amine value of 13 mgKOH/g (solid concentration: 52% by mass))
DFA: N,N-dimethylformamide dimethylacetal DPCA-60: "KAYARAD" (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.; ε-caprolactone-modified dipenta, having six oxypentylene carbonyl structures in the molecule erythritol hexaacrylate)
DPHA: "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku; dipentaerythritol hexaacrylate)
EGME: ethylene glycol bis(2-mercaptoethyl) ether GMA: glycidyl methacrylate HABI-102: 2,2′,5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4′,5 '-diphenyl-1,2'-biimidazole (manufactured by Tronly; biimidazole-based photopolymerization initiator)
HA: N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3-aminobenzoamide)
IC-379EG: "IRGACURE" (registered trademark) 379EG (manufactured by BASF; 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one; α-aminoketone system photoinitiator)
IC-819: "IRGACURE" (registered trademark) 819 (manufactured by BASF; bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide; acylphosphine oxide photopolymerization initiator)
IDN-1: 1,1-bis[4-(2-acryloxyethoxy)phenyl]indane IGZO: indium gallium zinc oxide ITO: indium tin oxide MAA: methacrylic acid MAP: 3-aminophenol; meta-aminophenol MBA: 3 - methoxy-n-butyl acetate MeTMS: methyltrimethoxysilane MgAg: Magnesium-Argentum (magnesium-silver alloy)
NA: 5-norbornene-2,3-dicarboxylic anhydride; nadic anhydride NC-7300L: epoxy resin having structural units containing a naphthalene skeleton, a benzene skeleton, and two epoxy groups (manufactured by Nippon Kayaku Co., Ltd.)
NMP: N-methyl-2-pyrrolidone ODPA: bis (3,4-dicarboxyphenyl) ether dianhydride; oxydiphthalic dianhydride OXE-02: "IRGACURE" (registered trademark) OXE-02 (manufactured by BASF; 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime; oxime ester photopolymerization initiator)
P. B. 15:6: C.I. I. pigment blue 15:6
P. B. 60: C.I. I. pigment blue 60
P. O. 43: C.I. I. pigment orange 43
P. R. 179:C. I. pigment red 179
P. R. 254: C.I. I. pigment red 254
P. V. 23: C.I. I. pigment violet 23
P. V. 37: C.I. I. pigment violet 37
P. Y. 139:C. I. pigment yellow 139
P. Y. 192:C. I. pigment yellow 192
PGMEA: propylene glycol monomethyl ether acetate PHA: phthalic anhydride PhTMS: phenyltrimethoxysilane S-20000: "SOLSPERSE" (registered trademark) 20000 (manufactured by Lubrizol; amine value is 32 mg KOH / g (solid concentration: 100 mass% ) Polyoxyalkylene ether-based dispersant having a tertiary amino group)
SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane STR: styrene TCDM: tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate; dimethylol-tricyclodecanedimeta Acrylate THPHA: 1,2,3,6-tetrahydrophthalic anhydride TMAH: Tetramethylammonium hydroxide TMOS: Tetramethoxysilane TMMP: Trimethylolpropane tris(3-mercaptopropionate)
TPK-1227: carbon black that has been surface-treated to introduce sulfonic acid groups (manufactured by CABOT)
WR-301: "ADEKA ARKLS" (registered trademark) WR-301 (manufactured by ADEKA; a resin obtained by ring-opening addition reaction of an aromatic compound having an epoxy group and an unsaturated carboxylic acid is reacted with a carboxylic acid anhydride. Polycyclic side chain-containing resin obtained by

Synthesis example (A)
18.31 g (0.05 mol) of BAHF, 17.42 g (0.3 mol) of propylene oxide, and 100 mL of acetone were weighed and dissolved in a three-necked flask. A solution of 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 10 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50°C. 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of 2-methoxyethanol, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and reacted at room temperature for 2 hours. After 2 hours, it was confirmed that the balloon had not deflated any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by distillation under reduced pressure to obtain a hydroxy group-containing diamine compound (HA) having the following structure.

Synthesis Example 1 Synthesis of Polyimide (PI-1) In a three-necked flask under a stream of dry nitrogen, 31.13 g (0.085 mol; 77.3 mol% of structural units derived from all amines and derivatives thereof) of BAHF, SiDA 1.24 g (0.0050 mol; 4.5 mol% with respect to structural units derived from all amines and derivatives thereof), and 2.18 g (0.020 mol; MAP) as a terminal blocking agent (0.020 mol; 18.2 mol % with respect to the derived structural unit), and 150.00 g of NMP was weighed and dissolved. Here, a solution of 31.02 g of ODPA (0.10 mol; 100 mol% relative to structural units derived from all carboxylic acids and derivatives thereof) dissolved in 50.00 g of NMP was added, stirred at 20°C for 1 hour, and then Stirred at 50° C. for 4 hours. After that, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while azeotroping water with the xylene. After completion of the reaction, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was obtained by filtration. The obtained solid was washed with water three times and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (PI-1). The resulting polyimide had an Mw of 27,000 and an acid equivalent of 350.

Synthesis Examples 2 to 5 Synthesis of polyimide (PI-2) to polyimide (PI-5) The monomer species and their ratios shown in Table 1-1 were polymerized in the same manner as in Synthesis Example 1 to obtain polyimide (PI- 2) ~ A polyimide (PI-5) was obtained.

Synthesis Example 6 Synthesis of Polyimide Precursor (PIP-1) In a three-necked flask under a stream of dry nitrogen, 44.42 g (0.10 mol; 100 mol% relative to structural units derived from all carboxylic acids and derivatives thereof) of 6FDA, 150 g of NMP was weighed and dissolved. Here, to 50 g of NMP, 14.65 g of BAHF (0.040 mol; 32.0 mol % based on structural units derived from all amines and their derivatives), 18.14 g of HA (0.030 mol; based on all amines and their derivatives) 24.0 mol% based on the structural units derived from) and 1.24 g of SiDA (0.0050 mol; 4.0 mol% based on the structural units derived from all amines and derivatives thereof) dissolved therein, and the mixture was heated to 20°C. for 1 hour and then at 50° C. for 2 hours. Next, as a terminal blocking agent, a solution of 5.46 g (0.050 mol; 40.0 mol% relative to the structural units derived from all amines and derivatives thereof) of MAP dissolved in 15 g of NMP was added, and Stirred for hours. After that, a solution of 23.83 g (0.20 mol) of DFA dissolved in 15 g of NMP was added dropwise over 10 minutes. After completion of dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and then poured into 3 L of water, and a solid precipitate was obtained by filtration. The obtained solid was washed with water three times and dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide precursor (PIP-1). The resulting polyimide precursor had an Mw of 20,000 and an acid equivalent of 450.

Synthesis Example 7 Synthesis of Polyimide Precursor (PIP-2) Polyimide precursor (PIP-2) was obtained by polymerization in the same manner as in Synthesis Example 6 using the monomer species and their ratios shown in Table 1-1. .

Synthesis Example 8 Synthesis of Polybenzoxazole (PBO-1) In a 500 mL round-bottomed flask equipped with a Dean-Stark water separator and condenser filled with toluene, 34.79 g (0.095 mol; 95.0 mol% based on structural units derived from), 1.24 g of SiDA (0.0050 mol; 5.0 mol% based on structural units derived from all amines and derivatives thereof), and 75.00 g of NMP. , dissolved. Here, in 25.00 g of NMP, 19.06 g of BFE (0.080 mol; 66.7 mol% with respect to structural units derived from all carboxylic acids and derivatives thereof), 6.57 g of NA as a terminal blocking agent (0 040 mol; 33.3 mol % based on structural units derived from all carboxylic acids and derivatives thereof) was added, stirred at 20°C for 1 hour, and then stirred at 50°C for 1 hour. After that, the mixture was heated and stirred at 200° C. or higher for 10 hours in a nitrogen atmosphere to carry out a dehydration reaction. After completion of the reaction, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was obtained by filtration. The obtained solid was washed with water three times and dried in a vacuum dryer at 80° C. for 24 hours to obtain polybenzoxazole (PBO-1). The resulting polybenzoxazole had an Mw of 25,000 and an acid equivalent of 330.

Synthesis Example 9 Synthesis of Polybenzoxazole Precursor (PBOP-1) In a 500 mL round-bottom flask equipped with a Dean-Stark water separator and condenser filled with toluene, 34.79 g (0.095 mol; total amines and their 95.0 mol% relative to structural units derived from derivatives), 1.24 g of SiDA (0.0050 mol; 5.0 mol% relative to structural units derived from all amines and derivatives thereof), and 70.00 g of NMP. and dissolved. Here, a solution of 19.06 g of BFE (0.080 mol; 66.7 mol% relative to structural units derived from all carboxylic acids and derivatives thereof) dissolved in 20.00 g of NMP was added and stirred at 20°C for 1 hour. and then stirred at 50° C. for 2 hours. Next, as a terminal blocking agent, a solution of 6.57 g of NA (0.040 mol; 33.3 mol% relative to structural units derived from all carboxylic acids and derivatives thereof) dissolved in 10 g of NMP was added, and Stirred for hours. After that, the mixture was stirred at 100° C. for 2 hours in a nitrogen atmosphere. After completion of the reaction, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was obtained by filtration. The resulting solid was washed with water three times and dried in a vacuum dryer at 80° C. for 24 hours to obtain a polybenzoxazole precursor (PBOP-1). The resulting polybenzoxazole precursor had an Mw of 20,000 and an acid equivalent of 330.

Synthesis Example 10 Synthesis of polysiloxane solution (PS-1) In a three-neck flask, 20.43 g (30 mol%) of MeTMS, 49.57 g (50 mol%) of PhTMS, 12.32 g (10 mol%) of cyEpoTMS, and 7 g of TMOS .61 g (10 mol %) and 83.39 g of PGMEA were charged. Air was flowed into the flask at 0.05 L/min, and the mixed solution was heated to 40°C in an oil bath while stirring. While further stirring the mixed solution, a phosphoric acid aqueous solution prepared by dissolving 0.270 g of phosphoric acid in 28.83 g of water was added dropwise over 10 minutes. After the dropwise addition was completed, the mixture was stirred at 40° C. for 30 minutes to hydrolyze the silane compound. After completion of hydrolysis, the bath temperature was raised to 70°C and the mixture was stirred for 1 hour, and then the bath temperature was raised to 115°C. After about 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (the internal temperature was 100 to 110° C.). The resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath to obtain a polysiloxane solution (PS-1). Mw of the resulting polysiloxane was 4,500.

Synthesis Example 11 Synthesis of polysiloxane solution (PS-2) 27.24 g (40 mol%) of MeTMS, 49.57 g (50 mol%) of PhTMS, 12.32 g (10 mol%) of cyEpoTMS, and 83 g of PGMEA were placed in a three-necked flask. 91g was charged. Air was flowed into the flask at 0.05 L/min, and the mixed solution was heated to 40°C in an oil bath while stirring. While further stirring the mixed solution, a phosphoric acid aqueous solution prepared by dissolving 0.267 g of phosphoric acid in 27.93 g of water was added over 10 minutes. After the addition was completed, the mixture was stirred at 40° C. for 30 minutes to hydrolyze the silane compound. After completion of hydrolysis, the bath temperature was raised to 70°C and the mixture was stirred for 1 hour, and then the bath temperature was raised to 115°C. After about 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 2 hours (the internal temperature was 100 to 110° C.). The resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath to obtain a polysiloxane solution (PS-2). Mw of the resulting polysiloxane was 4,000.

Synthesis Example 12 Synthesis of Polycyclic Side Chain-Containing Resin Solution (CR-1) 35.04 g (0.10 mol) of BHPF and 40.31 g of MBA were weighed and dissolved in a three-necked flask. A solution prepared by dissolving 27.92 g (0.090 mol) of ODPA in 30.00 g of MBA and 2.96 g (0.020 mol) of PHA as a terminal blocker was added thereto and stirred at 20° C. for 1 hour. After that, the mixture was stirred at 150° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the resulting solution was mixed with 10.00 g of MBA, 14.22 g (0.10 mol) of GMA, 0.135 g (0.0010 mol) of dibenzylamine, and 0.037 g (0.0003 mol) of 4-methoxyphenol. ) was added and stirred at 90° C. for 4 hours to obtain a polycyclic side chain-containing resin solution (CR-1). The resulting polycyclic side chain-containing resin had an Mw of 4,000, a carboxylic acid equivalent of 810 g/mol, and a double bond equivalent of 810 g/mol.

Synthesis Example 13 Synthesis of Polycyclic Side Chain-Containing Resin Solution (CR-2) In a three-necked flask, 46.25 g (0.10 mol) of BGPF and 54.53 g of MBA were weighed and dissolved. Here, a solution of 10.00 g of MBA, 17.22 g (0.20 mol) of MAA, 0.135 g (0.0010 mol) of dibenzylamine, and 0.037 g (0.0003 mol) of 4-methoxyphenol was added. and 90° C. for 4 hours. Thereafter, a solution of 27.92 g (0.090 mol) of ODPA dissolved in 30.00 g of MBA and 2.96 g (0.020 mol) of PHA as a terminal blocker was added and stirred at 20° C. for 1 hour. After that, the mixture was stirred at 150° C. for 5 hours in a nitrogen atmosphere to obtain a polycyclic side chain-containing resin solution (CR-2). The resulting polycyclic side chain-containing resin had an Mw of 4,700, a carboxylic acid equivalent of 470 g/mol, and a double bond equivalent of 470 g/mol.

Synthesis Example 14 Synthesis of Acid-Modified Epoxy Resin Solution (AE-1) 42.00 g of NC-7300L (epoxy equivalent: 210 g/mol) and 47.91 g of MBA were weighed and dissolved in a three-necked flask. Here, a solution of 10.00 g of MBA, 17.22 g (0.20 mol) of MAA, 0.270 g (0.0020 mol) of dibenzylamine, and 0.074 g (0.0006 mol) of 4-methoxyphenol was added. and 90° C. for 4 hours. After that, a solution of 24.34 g (0.160 mol) of THPHA dissolved in 30.00 g of MBA was added and stirred at 20° C. for 1 hour. After that, the mixture was stirred at 150° C. for 5 hours in a nitrogen atmosphere to obtain an acid-modified epoxy resin solution (AE-1). The resulting acid-modified epoxy resin had an Mw of 5,000, an acid equivalent of 510 g/mol, and a double bond equivalent of 410 g/mol.

Synthesis Example 15 Synthesis of Acrylic Resin Solution (AC-1) A three-necked flask was charged with 0.821 g (1 mol %) of 2,2′-azobis(isobutyronitrile) and 29.29 g of PGMEA. Next, 21.52 g (50 mol%) of MAA, 22.03 g (20 mol%) of TCDM, and 15.62 g (30 mol%) of STR are charged, stirred at room temperature for a while, and the inside of the flask is sufficiently replaced with nitrogen by bubbling. After that, the mixture was stirred at 70°C for 5 hours. Next, 59.47 g of PGMEA, 14.22 g (20 mol %) of GMA, 0.676 g (1 mol %) of dibenzylamine, and 0.186 g (0.3 mol %) of 4-methoxyphenol were added to the resulting solution. ) was added and stirred at 90° C. for 4 hours to obtain an acrylic resin solution (AC-1). The obtained acrylic resin had an Mw of 15,000, a carboxylic acid equivalent of 490 g/mol, and a double bond equivalent of 740 g/mol.

The compositions of Synthesis Examples 1 to 15 described above are collectively shown in Tables 1-1 to 1-3.

Coating Example 1 Synthesis of surface-coated benzofuranone-based black pigment (Bk-CBF1) As a black pigment, 150 g of a benzofuranone-based black pigment Bk-S0100CF (surface untreated; pigment surface pH 4.5) was The mixture was put into a glass container filled with ionized water and stirred with a dissolver to obtain an aqueous pigment suspension. This was sucked up with a tube pump, and sent into a horizontal bead mill filled with 0.4 mmφ zirconia beads (“Torayceram” (registered trademark); manufactured by Toray Industries, Inc.) for two-pass dispersion treatment. The entire amount was discharged into the inside and stirred again with the dissolver. A pH meter is set so that its tip electrode is immersed in a glass container at a depth of 3 to 5 cm from the liquid surface of the water-based pigment suspension being stirred, and the pH of the water-based pigment suspension thus obtained is measured. As a result of measurement, it showed pH 4.5 (liquid temperature 25°C). Thereafter, the liquid temperature of the water-based pigment suspension was raised to 60° C. while stirring. After 30 minutes, the stirring was temporarily stopped. After 2 minutes, it was confirmed that there was no sediment on the bottom of the glass container, and the stirring was resumed. .

An aqueous sodium _{silicate solution (Na 2 O.nSiO 2.mH 2} O; 30% by mass as sodium oxide, 10% by mass as silicon dioxide) diluted 100 times with deionized water, and 0.001 mol/L sulfuric acid, and the pH is maintained in the range of 2 or more and less than 7. The black pigment particles were coated by depositing silica on the surfaces of the black pigment particles. Next, with respect to the aqueous pigment suspension _, a sodium aluminate _aqueous solution (Na ₂ O. nAl ₂ O ₃ ·mH ₂ O; 40% by mass as sodium oxide, 50% by mass as alumina) diluted 100 times with deionized water and 0.001 mol/L sulfuric acid, pH 2 or more and less than 7 were added in parallel while adjusting the respective addition rates so as to be maintained within the range of . Subsequently, filtration and water washing operations are repeated three times to remove some of the water-soluble impurities in the aqueous pigment suspension, and the liquid is fed into a horizontal bead mill filled with 0.4 mmφ zirconia beads for one-pass dispersion treatment. bottom. Furthermore, in order to remove ionic impurities, 10 g each of a cation exchange resin and an anion exchange resin (Amberlite; manufactured by Organo Co., Ltd.) were added to the aqueous pigment suspension, stirred for 12 hours, and filtered to obtain a black filter. got stuff After drying this in a drying oven at 90° C. for 6 hours and in a drying oven at 200° C. for 30 minutes, it was granulated by dry pulverization using a jet mill to obtain a surface-coated benzofuranone-based black pigment (Bk-CBF1). Obtained.

As a result of analysis by time-of-flight secondary ion mass spectrometry and X-ray diffraction, the coating amount of silica and alumina of the obtained surface-coated benzofuranone-based black pigment (Bk-CBF1) is, respectively, per 100 parts by mass of black pigment. The amount was 10.0 parts by mass in terms of SiO ₂ and 2.0 parts by mass in terms of Al ₂ O ₃ , and the average coverage of the coating layer with respect to the pigment was 97.5%.

Preparation Example 1 Preparation of Pigment Dispersion (Bk-1) 34.5 g of S-20000 as a dispersant and 782.0 g of MBA as a solvent are weighed and mixed, stirred for 10 minutes to diffuse, and then a colorant. Then, weigh 103.5 g of Bk-S0100CF, mix and stir for 30 minutes, and use a horizontal bead mill filled with 0.40 mmφ zirconia beads to obtain a number average particle size of 100 nm. Wet media dispersion treatment. to obtain a pigment dispersion (Bk-1) having a solid content concentration of 15% by mass and a colorant/dispersant ratio of 75/25 (mass ratio). The number average particle size of the pigment in the resulting pigment dispersion was 100 nm.

Preparation Example 2 Preparation of Pigment Dispersion Liquid (Bk-2) As the resin, 92.0 g of the 30% by mass MBA solution of the polyimide (PI-1) obtained in Synthesis Example 1, and as the dispersant, S-20000. 27.6 g and 717.6 g of MBA as a solvent were weighed and mixed, stirred for 10 minutes to diffuse, and then 82.8 g of Bk-S0100CF as a coloring agent were weighed and mixed, stirred for 30 minutes, and Using a horizontal bead mill filled with zirconia beads of 40 mmφ, wet media dispersion treatment is performed so that the number average particle diameter is 100 nm, the solid content concentration is 15% by mass, and the colorant/resin/dispersant = 60/20. /20 (mass ratio) to obtain a pigment dispersion (Bk-2). The number average particle size of the pigment in the resulting pigment dispersion was 100 nm.

Preparation Examples 3 to 18 Preparation of Pigment Dispersion (Bk-3) to Pigment Dispersion (Bk-18) Types of colorant, (A1) first resin and (E) dispersant described in Table 2-1, and At these ratios, the pigment was dispersed in the same manner as in Preparation Example 2 to obtain Pigment Dispersion (Bk-3) to Pigment Dispersion (Bk-18).

The compositions of Preparation Examples 1 to 18 are collectively shown in Table 2-1.

As the (Da) black agent, the coloring agent Bk-S0100CF contained in the pigment dispersions (Bk-1) to (Bk-3), the Bk-S0084 contained in the pigment dispersion (Bk-4), and the pigment The maximum transmission wavelengths of the colorants (mixture of PR 179, PY 192 and PB 60) contained in the dispersion (Bk-9) are shown below.
Bk-S0100CF: 340nm
Bk-S0084: 350 nm
P. R. 179, p. Y. 192 and P.S. B. 60 mixture: 390 nm

A list of (C1-1) specific oxime ester photopolymerization initiators used in Examples and Comparative Examples and oxime ester photopolymerization initiators (OXL-A and OXE-02) used in Comparative Examples, and The physical property values are summarized in Tables 2-2 and 2-3.

The structural formulas of (C1-1) the specific oxime ester photopolymerization initiator and the oxime ester photopolymerization initiators (OXL-A and OXE-02) used in Comparative Examples are shown below.

The structural units possessed by the acid-modified epoxy resin (AE-1) obtained in Synthesis Example 14 are shown below. Acid-modified epoxy resin (AE-1) has a structural unit represented by general formula (38a).

Evaluation methods in each example and comparative example are shown below.

(1) Weight average molecular weight of resin Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation), using tetrahydrofuran or NMP as a fluidized bed, based on "JIS K7252-3 (2008)", a method at around room temperature. was obtained by measuring the weight average molecular weight in terms of polystyrene.

(2) Acid value, acid equivalent Using a potentiometric automatic titrator (AT-510; manufactured by Kyoto Electronics Industry Co., Ltd.), 0.1 mol / L sodium hydroxide / ethanol solution as a titration reagent, xylene / N, N as a titration solvent - Using dimethylformamide = 1/1 (mass ratio), based on "JIS K2501 (2003)", the acid value (unit: mgKOH/g) was measured by potentiometric titration. The acid equivalent (unit: g/mol) was calculated from the measured acid value.

(3) Double bond equivalent Using a potentiometric automatic titrator (AT-510; manufactured by Kyoto Electronics Industry Co., Ltd.), an iodine monochloride solution (iodine trichloride = 7.9 g, iodine = 8.9 g, acetic acid = 1,000 mL mixed solution), a 100 g / L potassium iodide aqueous solution as an unreacted iodine capture aqueous solution, and a 0.1 mol / L sodium thiosulfate aqueous solution as a titration reagent, JIS K0070: 1992 "Chemical product acid The iodine value of the resin was measured by the Wiiss method based on the method described in "6. . The double bond equivalent (unit: g/mol) was calculated from the measured iodine value (unit: gI/100 g).

(4) Content ratio of each organosilane unit in polysiloxane
²⁹ Si-NMR was measured to calculate the ratio of the integrated value of Si derived from a specific organosilane unit to the integrated value of all Si derived from the organosilane, and their content ratios were calculated. A sample (liquid) was injected into a "Teflon" (registered trademark) NMR sample tube with a diameter of 10 mm and used for measurement. ²⁹ Si-NMR measurement conditions are shown below.
Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nucleus frequency: 53.6693 MHz ( ²⁹ Si nuclei)
Spectrum width: 20000Hz
Pulse width: 12 μs (45° pulse)
Pulse repetition time: 30.0 seconds Solvent: Acetone-d6
Reference substance: Tetramethylsilane Measurement temperature: 23°C
Sample rotation speed: 0.0 Hz.

(5) Number average particle size of pigment Using a zeta potential/particle size/molecular weight measuring device (Zetasizer Nano ZS; manufactured by Sysmex Corporation), using PGMEA as a dilution solvent, a pigment dispersion liquid of 1.0 × 10 ^-5 Dilute to a concentration of ~40% by volume, set the refractive index of the diluted solvent to the refractive index of PGMEA, set the refractive index of the measurement target to 1.6, and irradiate a laser beam with a wavelength of 633 nm to The number average particle size of the pigment was measured.

(6) Substrate pretreatment A glass substrate (manufactured by Geomatec; hereinafter referred to as "ITO substrate") having a 100 nm film of ITO formed on the glass by sputtering was treated with a tabletop optical surface treatment device (PL16-110; Sen Special Light Source Co., Ltd.). was used after UV-O ₃ cleaning treatment for 100 seconds. A Si wafer (manufactured by Electronics End Materials Corporation) was used after dehydration baking by heating at 130° C. for 2 minutes using a hot plate (HP-1SA; manufactured by AS ONE).

(7) Film thickness measurement Using a surface roughness/contour shape measuring machine (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the measurement magnification is 10,000 times, the measurement length is 1.0 mm, and the measurement speed is 0.30 mm/s. As such, the film thickness was measured after prebaking, after development, and after heat curing.

(8) Sensitivity A grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS) is measured using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) by the method described in Example 1 below. ; manufactured by Opto-Line International), patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp, then a small developing device for photolithography (AD- 2000; manufactured by Takizawa Sangyo Co., Ltd.) to prepare a film after development of the negative photosensitive resin composition.

Using an FPD/LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolution pattern of the prepared film after development was observed, and the exposure dose to form a 20 μm line-and-space pattern with a width of 1:1. (Value of i-line illuminance meter) was defined as sensitivity. Determined as follows, A +, A, B, and C with a sensitivity of 90 mJ/cm ² or less were accepted, A +, A, and B with a sensitivity of 60 mJ/cm ² or less were considered good sensitivity, A+ and A, which had a sensitivity of 45 mJ/cm ² or less, were considered excellent in sensitivity.
A+: sensitivity is 1 to 30 mJ/cm ²
A: Sensitivity is 31 to 45 mJ/cm ²
B: Sensitivity is 46 to 60 mJ/cm ²
C: sensitivity of 61 to 90 mJ/cm ²
D: Sensitivity is 91 to 150 mJ/cm ²
E: Sensitivity of 151 to 500 mJ/cm ² .

(9) Development residue below, by the method described in Example 1, using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.), a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5- After patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp via FS; manufactured by Opto-Line International), a small developing device for photolithography ( After development using AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) was used to prepare a film after development of the negative photosensitive resin composition. .

Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolution pattern of the prepared cured film is observed, and the presence or absence of pigment-derived residues in the openings of the 20 μm line and space pattern is observed. bottom. Judging as follows, A+, A, and B where the area where the residue exists in the opening is 10% or less are accepted, and A+ and A where the area where the residue exists in the opening is 5% or less are developed. Residue was judged to be good, and A+, in which there was no residual area in the opening, was judged to be excellent in development residue.
A+: No residue in the opening A: Residue existing area in the opening is 1 to 5%
B: The area where the residue exists in the opening is 6 to 10%
C: The area where the residue exists in the opening is 11 to 30%
D: The area where the residue exists in the opening is 31 to 50%
E: Residue existing area in the opening is 51 to 100%.

(10) Pattern cross-sectional shape after development Using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) according to the method described in Example 1 below, a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), patterning exposure with ultra-high pressure mercury lamp i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm), then for photolithography Development was performed using a compact developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) to prepare a film after development of the negative photosensitive resin composition.

A field emission scanning electron microscope (S-4800; manufactured by Hitachi High-Technologies Corporation) was used to observe the cross section of a line-and-space pattern with a space dimension width of 20 μm among the resolved patterns of the film after development, The taper angle of the cross section was measured. Judging as follows, A +, A, and B with a cross-sectional taper angle of 60 ° or less are accepted, A + and A with a cross-sectional taper angle of 45 ° or less are good, and A + and A are good pattern shapes. A+, which has a taper angle of 30° or less, was regarded as having an excellent pattern shape.
A+: The taper angle of the cross section is 1 to 30°
A: The taper angle of the cross section is 31 to 45°
B: Taper angle of cross section is 46 to 60°
C: Taper angle of cross section is 61 to 70°
D: Taper angle of cross section is 71 to 80°
E: The taper angle of the cross section is 81 to 179°.

(11) Pattern cross-sectional shape after heat curing Using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) according to the method described in Example 1 below, a grayscale mask (MDRM) for sensitivity measurement MODEL 4000-5-FS; manufactured by Opto-Line International), patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp, followed by photolithography. After developing using a small developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), a negative photosensitive resin composition is cured using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). A membrane was prepared.

Using a field emission scanning electron microscope (S-4800; manufactured by Hitachi High-Technologies Corporation), among the resolution patterns of the prepared cured film, the cross section of the line and space pattern with a space dimension width of 20 μm was observed. was measured. Judging as follows, A +, A, and B with a cross-sectional taper angle of 60 ° or less are accepted, A + and A with a cross-sectional taper angle of 45 ° or less are good, and A + and A are good pattern shapes. A+, which has a taper angle of 30° or less, was regarded as having an excellent pattern shape.
A+: The taper angle of the cross section is 1 to 30°
A: The taper angle of the cross section is 31 to 45°
B: Taper angle of cross section is 46 to 60°
C: Taper angle of cross section is 61 to 70°
D: Taper angle of cross section is 71 to 80°
E: The taper angle of the cross section is 81 to 179°.

(12) Change in pattern opening dimension width before and after heat curing, using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) according to the method described in Example 1 below, gray scale for sensitivity measurement Through a mask (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), patterning exposure was performed with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp. After that, development was performed using a compact developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) to prepare a film after development of the negative photosensitive resin composition.

Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolution pattern of the film after development was observed, and the opening dimension width of the line and space pattern of 20 μm was measured. pattern opening dimension width (CD _DEV ).

After that, the above-described developed film is thermally cured by the method described in Example 1 below using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a negative photosensitive resin composition. A cured film was produced.

Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolution pattern of the prepared cured film was observed, and the opening size of the 20 μm line and space pattern at the same location as the location observed after development. The width was measured and used as the pattern opening dimension width (CD _CURE ) after thermal curing.

From the pattern opening dimension width after development and the pattern opening dimension width after heat curing, the change in the pattern opening dimension width before and after heat curing ((CD _DEV )−(CD _CURE )) was calculated. A+, A, and B where the change in the pattern opening dimension width before and after heat curing is 0.60 μm or less are judged as follows, and the pattern opening dimension width change before and after heat curing is 0.40 μm or less. A+ and A were defined as good change in pattern dimension width, change in pattern opening dimension width before and after heat curing was 0.20 μm or less, and A+ was defined as excellent pattern dimension width change.
A+: Change in pattern opening dimension width before and after heat curing is 0 to 0.20 μm
A: Change in pattern opening dimension width before and after heat curing is 0.21 to 0.40 μm
B: Change in pattern opening dimension width before and after heat curing is 0.41 to 0.60 μm
C: Change in pattern opening dimension width before and after heat curing is 0.61 to 1.00 μm
D: Change in pattern opening dimension width before and after heat curing is 1.01 to 2.00 μm
E: Change in pattern opening dimension width before and after heat curing is 2.01 μm or more.

(13) Heat resistance (high-temperature weight residual rate difference)
A grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; Opto-Line International Co.), after patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp, a compact developing device for photolithography (AD-2000; Takizawa (manufactured by Sangyo Co., Ltd.), and then a cured film of the negative photosensitive resin composition was prepared using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.).

After thermal curing, about 10 mg of the prepared cured film was scraped off from the substrate and placed in an aluminum cell. Using a thermogravimetric measuring device (TGA-50; manufactured by Shimadzu Corporation), the aluminum cell was held in a nitrogen atmosphere at 30°C for 10 minutes, and then heated to 150°C at a heating rate of 10°C/min. After that, the temperature was maintained at 150° C. for 30 minutes, and thermogravimetric analysis was performed while the temperature was increased to 500° C. at a temperature increase rate of 10° C./min. The weight residual rate at 350 ° C. when further heated is (M _a ) mass %, and the weight residual rate at 400 ° C. is (M _b ) mass with respect to the weight 100 mass % after heating at 150 ° C. for 30 minutes. %, and as an index of heat resistance, the high-temperature weight residual rate difference ((M _a )−(M _b )) was calculated.

Determined as follows, A +, A, and B with a high-temperature weight residual rate difference of 25.0% by mass or less are accepted, and A + and A with a high-temperature weight residual rate difference of 15.0% or less. A+ was judged to be excellent in heat resistance when the heat resistance was good and the difference in high-temperature weight residual rate was 5.0% or less.
A+: high temperature weight residual rate difference is 0 to 5.0%
A: High temperature weight residual rate difference is 5.1 to 15.0%
B: High temperature weight residual rate difference is 15.1 to 25.0%
C: High-temperature weight residual rate difference is 25.1 to 35.0%
D: High-temperature weight residual rate difference is 35.1 to 45.0%
E: High-temperature weight residual rate difference is 45.1 to 100%.

(14) Light shielding property (optical density (hereinafter, “OD”) value)
A grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; Opto-Line International Co.), after patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp, a compact developing device for photolithography (AD-2000; Takizawa (manufactured by Sangyo Co., Ltd.), and then a cured film of the negative photosensitive resin composition was prepared using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.).

Using a transmission densitometer (X-Rite 361T(V); manufactured by X-Rite), the incident light intensity (I ₀ ) and transmitted light intensity (I) of the prepared cured film were measured. As an indicator of the light shielding property, the OD value was calculated by the following formula.
OD value = _log10 ( _I0 /I).

(15) Insulation (surface resistivity)
A grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; Opto-Line International Co.), after patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp, a compact developing device for photolithography (AD-2000; Takizawa (manufactured by Sangyo Co., Ltd.), and then a cured film of the negative photosensitive resin composition was prepared using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). The surface resistivity (Ω/□) of the prepared cured film was measured using a high resistance resistivity meter (“Hiresta” UP; manufactured by Mitsubishi Chemical Corporation).

(16) Light Emitting Characteristics of Organic EL Display (Method of Making Organic EL Display)
FIG. 4 shows a schematic diagram of the substrate used. First, an ITO transparent conductive film of 10 nm was formed on the entire surface of the alkali-free glass substrate 47 of 38×46 mm by sputtering, and etched as the first electrode 48 to form a transparent electrode. At the same time, an auxiliary electrode 49 was also formed to extract the second electrode (FIG. 4 (step 1)). The obtained substrate was ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water. Next, on this substrate, a negative photosensitive resin composition is applied and prebaked by the method described in Example 1, patterning exposure is performed through a photomask having a predetermined pattern, development and rinsing are performed, Heated and thermoset. By the above method, openings with a width of 70 μm and a length of 260 μm are arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposes the first electrode. It is formed only in the effective area of the substrate (FIG. 4 (step 2)). This opening will eventually become the luminescent pixel of the organic EL display. The effective area of the substrate is 16 mm square, and the thickness of the insulating layer 50 is about 1.0 μm.

Next, using the substrate on which the first electrode 48, the auxiliary electrode 49 and the insulating layer 50 were formed, an organic EL display was produced. After performing nitrogen plasma treatment as a pretreatment, an organic EL layer 51 including a light-emitting layer was formed by a vacuum deposition method (FIG. 4 (step 3)). The degree of vacuum during vapor deposition was 1×10 ⁻³ Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition. First, 10 nm of compound (HT-1) was deposited as a hole injection layer, and 50 nm of compound (HT-2) was deposited as a hole transport layer. Next, the compound (GH-1) as a host material and the compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm so that the doping concentration was 10%. After that, the compound (ET-1) and the compound (LiQ) as electron transport materials were laminated at a volume ratio of 1:1 to a thickness of 40 nm. Structures of compounds used in the organic EL layer are shown below.

Next, after vapor-depositing a compound (LiQ) to a thickness of 2 nm, MgAg (magnesium/silver=10/1 (volume ratio)) was vapor-deposited to a thickness of 100 nm to form a second electrode 52, forming a reflective electrode (FIG. 4 (step 4) ). After that, in a low-humidity nitrogen atmosphere, a cap-shaped glass plate was adhered using an epoxy resin-based adhesive for sealing, and four 5 mm square bottom emission type organic EL displays were produced on one substrate. . The film thickness referred to herein is a value displayed by a crystal oscillation type film thickness monitor.

(Evaluation of emission characteristics)
The organic EL display manufactured by the method described above was made to emit light by direct-current driving at 10 mA/cm ² , and was observed for light emission defects such as non-light-emitting areas and luminance unevenness. The produced organic EL display was held at 80° C. for 500 hours as a durability test. After the durability test, the organic EL display was caused to emit light by direct current driving at 10 mA/cm ² , and it was observed whether or not there was any change in light emission characteristics such as light emission area and luminance unevenness. Judgment is made as follows, and when the light-emitting region area before the durability test is 100%, the light-emitting region area after the durability test is 80% or more, and A+, A, and B are passed, and the light-emitting region area is A+ and A with 90% or more were defined as good light emission characteristics, and A+ with a light emission area of 95% or more were defined as excellent light emission characteristics.
A+: 95 to 100% of the light-emitting area after the endurance test
A: Light-emitting region area after durability test is 90 to 94%
B: 80 to 89% of light-emitting area after durability test
C: 70 to 79% of light-emitting area after durability test
D: 50 to 69% of light-emitting area after durability test
E: 0 to 49% of the light-emitting area after the durability test.

[Example 1]
Under a yellow light, 0.152 g of OXL-21 was weighed, 7.274 g of MBA and 5.100 g of PGMEA were added and dissolved by stirring. Next, 6.566 g of 30% by mass MBA solution of polyimide (PI-1) obtained in Synthesis Example 1, 0.606 g of 50% by mass MBA solution of DPHA, 50% by mass of MBA of DPCA-60 1.515 g of the solution was added and stirred to obtain a preparation as a homogeneous solution. Next, 7.323 g of the pigment dispersion (Bk-1) obtained in Preparation Example 1 was weighed, and 17.677 g of the prepared liquid obtained by the method described above was added and stirred to form a uniform solution. bottom. Thereafter, the resulting solution was filtered through a 0.45 μmφ filter to prepare composition 1.

After applying the prepared composition 1 on the ITO substrate by spin coating at an arbitrary rotation speed using a spin coater (MS-A100; manufactured by Mikasa), a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE) was applied. was prebaked at 110° C. for 120 seconds to prepare a prebaked film having a film thickness of about 1.8 μm.

The prepared pre-baked film is spray-developed with a 2.38% by mass TMAH aqueous solution using a small developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), and the pre-baked film (unexposed area) is completely dissolved. (Breaking Point; hereinafter referred to as "B.P.") was measured.

A pre-baked film is prepared in the same manner as described above, and the prepared pre-baked film is applied to a gray scale mask (MDRM MODEL 4000-5) for sensitivity measurement using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co. -FS (manufactured by Opto-Line International), patterning exposure was performed with i-line (wavelength: 365 nm), h-line (wavelength: 405 nm), and g-line (wavelength: 436 nm) of an extra-high pressure mercury lamp. After exposure, using a compact developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), the film was developed with a 2.38% by mass TMAH aqueous solution and rinsed with water for 30 seconds. The development time is B.I. P. 1.5 times.

After development, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), it was thermally cured at 250° C. to prepare a cured film having a thickness of about 1.2 μm. As for the heat curing conditions, heat curing was performed at 250° C. for 60 minutes in a nitrogen atmosphere.

[Examples 2 to 83 and Comparative Examples 1 to 8]
Compositions 2 to 91 were prepared in the same manner as in Example 1 with the compositions shown in Tables 3-1 to 14-1. Using each of the obtained compositions, a composition was formed on a substrate in the same manner as in Example 1, and the photosensitive properties and properties of the cured film were evaluated. These evaluation results are summarized in Tables 3-2 to 14-2. For ease of comparison, Tables 4-1 to 5-1, Tables 7-1 to 13-1, Tables 4-2 to 5-2, and Tables 7-2 to 13-2 The composition and evaluation results of Example 7 are described respectively.

[Example 84]
(Manufacturing method of organic EL display without polarizing layer)
An outline of the organic EL display to be produced is shown in FIG. First, a laminated film of chromium and gold was formed on a non-alkali glass substrate 53 of 38×46 mm by electron beam evaporation, and a source electrode 54 and a drain electrode 55 were formed by etching. Next, APC (silver/palladium/copper = 98.07/0.87/1.06 (mass ratio)) was deposited by sputtering to a thickness of 100 nm, and patterned by etching to form an APC layer. An ITO film of 10 nm was formed on the upper layer of the layer by sputtering, and a reflective electrode 56 was formed as a first electrode by etching. After the electrode surface was washed with oxygen plasma, an amorphous IGZO film was formed by sputtering, and an oxide semiconductor layer 57 was formed between the source and drain electrodes by etching. Next, a film of a positive photosensitive polysiloxane material (SP-P2301; manufactured by Toray Industries, Inc.) is formed by spin coating, via holes 58 and pixel regions 59 are opened by photolithography, and then heat cured to form a gate. An insulating layer 60 was formed. After that, a gold film was formed by electron beam evaporation, and a gate electrode 61 was formed by etching to form an oxide TFT array.

By the method described in Example 1 above, the composition 7 is coated and pre-baked on the oxide TFT array to form a film, patterned through a photomask having a predetermined pattern, exposed to light, developed and rinsed to form a pixel region. was opened and then thermally cured to form a TFT protective layer/pixel dividing layer 62 having a light shielding property. By the above method, the pixel division layer was formed on the substrate with openings having a width of 70 μm and a length of 260 μm arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposing the reflective electrode. Formed only in the effective area. It should be noted that this opening will eventually become the light-emitting pixel of the organic EL display. The substrate effective area was 16 mm square, and the thickness of the pixel division layer was about 1.0 μm.

Next, by the method described in (16) above, the compound (HT-1) as the hole injection layer, the compound (HT-2) as the hole transport layer, the compound (GH-1) as the host material, and the dopant material An organic EL light-emitting layer 63 was formed using the compound (GD-1) and the compound (ET-1) and the compound (LiQ) as electron transport materials.

Thereafter, a film of MgAg (magnesium/silver=10/1 (volume ratio)) of 10 nm was formed by vapor deposition, and a transparent electrode 64 was formed as a second electrode by etching. Next, in a low humidity nitrogen atmosphere, a sealing film 65 was formed using an organic EL sealing material (Structbond (registered trademark) XMF-T; manufactured by Mitsui Chemicals, Inc.). Further, an alkali-free glass substrate 66 was bonded onto the sealing film, and four top emission type organic EL displays each having a size of 5 mm square and having no polarizing layer were produced on one substrate. The film thickness referred to herein is a value displayed by a crystal oscillation type film thickness monitor.

(Evaluation of emission characteristics)
The organic EL display manufactured by the method described above is driven to emit light by direct current driving at 10 mA/cm ² , the luminance (Y′) when the pixel division layer is irradiated with external light, and the luminance (Y′) when external light is not irradiated. Y ₀ ) was measured. Contrast was calculated by the following formula as an index of external light reflection reduction.
Contrast = _Y0 /Y'.

Determined as follows, A +, A, and B with a contrast of 0.80 or more are accepted, A + and A with a contrast of 0.90 or more are considered to have a good external light reflection reduction effect, and the contrast is 0. 0.95 or higher, A+ was considered excellent in the external light reflection reduction effect. It was confirmed that the organic EL display manufactured by the method described above had a contrast of 0.90 and could reduce external light reflection.
A+: Contrast is 0.95 to 1.00
A: Contrast is 0.90 to 0.94
B: Contrast is 0.80 to 0.89
C: Contrast is 0.70 to 0.79
D: Contrast is 0.50 to 0.69
E: Contrast is 0.01 to 0.49.

[Example 85]
(Evaluation of halftone characteristics)
A pre-baked film of composition 7 was formed on an ITO substrate to a thickness of 5 μm by the method described in Example 1, and a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) was used. Then, through a halftone photomask for evaluating halftone characteristics, the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm). 9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) was used to prepare a cured film of composition 7.

As the halftone photomask, a photomask having a light-transmitting portion, a light-shielding portion, and a semi-light-transmitting portion between the light-transmitting portion and the light-shielding portion was used. The transmittance (% T _HT )% of the translucent portion is 10%, 15%, 20%, 25%, 30%, 35%, and 40% of the transmittance (% T _FT ) of the translucent portion, respectively. , 45% and 50%. The translucent portion and the semi-translucent portion are adjacent, and the semi-translucent portion and the light shielding portion are adjacent. The pattern shapes of the light-transmitting portion, the semi-light-transmitting portion, and the light-shielding portion all have line-shaped portions. Both the translucent part and the light shielding part have a square-shaped part. The pattern dimensions of the light-transmitting portions are 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, or 100 μm. Moreover, the pattern size of the light shielding portion is 10 μm. On the other hand, the semi-transparent portions have pattern dimensions of 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm and 100 μm, respectively.

As an example of a halftone photomask, FIG. 6 shows an example of the arrangement and dimensions of the light-transmitting portion, the light-shielding portion, and the semi-light-transmitting portion.

Using a surface roughness / contour measuring machine (SURFCOM 1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the measurement magnification is 10,000 times, the measurement length is 1.0 mm, and the measurement speed is 0.30 mm / s. The film thickness after development and the film thickness (T _FT ) μm after thermosetting were measured. For the semi-transparent portion, the film thickness after development and the film thickness (T _HT ) μm after thermal curing at locations with different transmittances were measured, and the remaining film after development, after thermal curing of the semi-transparent portion, was measured. A minimum film thickness (T _HT/min ) μm was obtained. As an index of halftone characteristics, the maximum step film thickness was calculated by the following formula.
Maximum step film thickness = (T _FT )-(T _HT/min ).

A+, A, B, and C with a maximum step thickness of 1.0 μm or more are judged as follows, and A+, A, and B with a maximum step thickness of 1.5 μm or more are halftones. A+ and A having good characteristics and a maximum step thickness of 2.0 μm or more were evaluated as having excellent halftone characteristics. The cured film of Composition 7 prepared by the above method had a film thickness (T _FT ) of 4.0 μm after heat curing in the translucent portion, and a minimum film thickness (T _HT/min ) was 2.3 μm, the maximum step thickness was 1.7 μm, and it was confirmed that the halftone characteristics were good.
A+: The maximum step thickness is 2.5 μm or more A: The maximum step thickness is 2.0 μm or more and less than 2.5 μm B: The maximum step thickness is 1.5 μm or more and less than 2.0 μm C: The maximum step thickness is 1.0 μm or more and less than 1.5 μm D: Maximum step thickness is 0.5 μm or more and less than 1.0 μm E: Maximum step thickness is 0.1 μm or more and less than 0.5 μm F: Maximum step thickness is 0.5 μm or more Less than 1 μm or no film remaining after development, making measurement impossible.

In the same manner, compositions 18-35, 60-68, 1, 5, 43, 45, 47, 48, 51, 53, 54, 56-59, and 78-81 were used as Examples 86-129. , Comparative Examples 9 to 13, compositions 87, 88, 84, 90, and 89 were used to evaluate the halftone properties. The evaluation results of Examples 85-129 and Comparative Examples 9-13 are shown in Tables 15-1 and 15-2.

INDUSTRIAL APPLICABILITY The negative photosensitive resin composition, the cured film, the organic EL display, and the method for producing the same according to the present invention are suitable for organic EL displays with improved display characteristics and reliability.

1, 12, 15, 26 glass substrate 2, 16 TFT
3, 17 Cured film for flattening TFT 4 Reflective electrode 5a, 21a Pre-baked film 5b, 21b, 28 Cured pattern 6, 22 Mask 7, 23 Actinic radiation 8 EL emitting layer 9, 18, 64 Transparent electrode 10, 29 Flatness Cured film for curing 11 Cover glass 13 BLU
14 glass substrate with BLU 19 planarization film 20, 30 alignment film 24 glass substrate with BCS 25 glass substrate with BLU and BCS 27 color filter 31 color filter substrate 32 glass substrate with BLU, BCS and BM 33 liquid crystal layer 34 Thick film portions 35a, 35b, 35c Thin film portions 36a, 36b, 36c, 36d, 36e Inclined sides in the cross section of the cured pattern 37 Horizontal sides of underlying substrates 47, 53, 66 Alkali-free glass substrate 48 First electrode 49 Auxiliary electrode 50 Insulating layer 51 Organic EL layer 52 Second electrode 54 Source electrode 55 Drain electrode 56 Reflective electrode 57 Oxide semiconductor layer 58 Via hole 59 Pixel region 60 Gate insulating layer 61 Gate electrode 62 TFT protective layer/Pixel dividing layer 63 Organic EL light emitting layer 65 sealing film

Claims (24)

(A) an alkali-soluble resin, (C1) a photopolymerization initiator, and (Da) a negative photosensitive resin composition containing a black agent,
The (A) alkali-soluble resin is selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor. (A1) containing a first resin containing one or more types of
At least one selected from the group consisting of the (A1-1) polyimide, the (A1-2) polyimide precursor, the (A1-3) polybenzoxazole, and the (A1-4) polybenzoxazole precursor , having a structural unit having a fluorine atom in 10 to 100 mol% of all structural units,
The (C1) photopolymerization initiator contains (C1-1) an oxime ester photopolymerization initiator,
The (C1-1) oxime ester photopolymerization initiator has the structure (I),
The (C1-1) oxime ester photopolymerization initiator comprises a compound represented by general formula (12), a compound represented by general formula (13), and a compound represented by general formula (14). containing one or more selected from the group
Negative photosensitive resin composition.
(I) one or more structures selected from the group consisting of a naphthalenecarbonyl structure, a trimethylbenzoyl structure, a thiophenecarbonyl structure, and a furancarbonyl structure;

(In general formulas (12) to (14), X ¹ to X ⁶ are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or a cycloalkylene group having 4 to 10 carbon atoms. represents an arylene group of 1 to 15. Y ¹ to Y ³ each independently represent carbon, nitrogen, oxygen or sulfur, R ³¹ to R ³⁶ each independently represent an alkyl having 1 to 10 carbon atoms a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 ^to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon ^atoms . Each independently, a group represented by general formula (15), a group represented by general formula (16), a group represented by general formula (17), or a group represented by general formula (18) Each of R ⁴⁰ to R ⁴⁵ is independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or 4 to 10 carbon atoms. Each of R ⁴⁶ to R ⁴⁸ is independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms. , an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. R ⁴⁹ to R ⁵¹ each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group, R ⁵² to R ⁵⁴ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a represents an integer of 0 to 3, b represents 0 or 1, c represents an integer of 0 to 5, d represents 0 or 1, e represents an integer of 0 to 4 f represents an integer of 0 to 2; g, h, and i each independently represent an integer of 0 to 2; j, k, and l each independently represent 0 or 1 and m, n, and o each independently represent an integer from 0 to 10.)

(In general formulas (15) to (18), R55 to R58 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, represents an alkoxy group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms, a represents an integer of 0 to 7, b represents an integer of 0 to 2, and c and d are respectively independently represents an integer from 0 to 3.) In the general formulas (12) and (13), Y ¹ and Y ² each independently represents carbon or nitrogen, and in the general formula (14), Y ³ is sulfur, the negative photosensitive resin composition of claim 1. The (Da) black agent contains (D1a) a black pigment,
The (D1a) black pigment consists of (D1a-1) a benzofuranone-based black pigment, (D1a-1b) a perylene-based black pigment, and (D1a-1c) an azo-based black pigment as (D1a-1) a black organic pigment. containing one or more selected from the group,
The negative photosensitive resin composition according to claim 1 or 2 . The (D1a-1) black organic pigment contains (D1a-1a) a benzofuranone-based black pigment,
The negative photosensitive resin composition according to claim 3 . The (Da) black agent contains (D1a) a black pigment,
The (D1a) black pigment is (D1a-3) a coloring pigment mixture of two or more colors, (D1a-3a) a blue pigment, a red pigment, and a coloring pigment mixture containing a yellow pigment, (D1a-3b) a purple pigment and A colored pigment mixture containing a yellow pigment, (D1a-3c) a colored pigment mixture containing a blue pigment, a red pigment, and an orange pigment, or (D1a-3d) a blue pigment, a purple pigment, and a colored pigment mixture containing an orange pigment. hand,
The blue pigment is C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, and C.I. I. One or more selected from the group consisting of Pigment Blue 60,
The red pigment is C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179, and C.I. I. One or more selected from the group consisting of Pigment Red 190,
The yellow pigment is C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 192, and C.I. I. One or more selected from the group consisting of Pigment Yellow 194,
The purple pigment is C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 29, and C.I. I. One or more selected from the group consisting of Pigment Violet 37,
The orange pigment is C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, and C.I. I. one or more selected from the group consisting of Pigment Orange 72;
The negative photosensitive resin composition according to any one of claims 1 to 4 . Furthermore, (D1b-1) contains at least one selected from the group consisting of blue pigments, red pigments, yellow pigments, purple pigments, orange pigments, and green pigments as organic pigments other than black,
The blue pigment is C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, and C.I. I. One or more selected from the group consisting of Pigment Blue 60,
The red pigment is C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179, and C.I. I. One or more selected from the group consisting of Pigment Red 190,
The yellow pigment is C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 192, and C.I. I. One or more selected from the group consisting of Pigment Yellow 194,
The purple pigment is C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 29, and C.I. I. One or more selected from the group consisting of Pigment Violet 37,
The orange pigment is C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, and C.I. I. one or more selected from the group consisting of Pigment Orange 72;
The negative photosensitive resin composition according to any one of claims 1 to 4 . The (C1-1) oxime ester photopolymerization initiator further has one or more structures selected from the group consisting of (II) and (III), according to any one of claims 1 to 6. A negative photosensitive resin composition.
(II) a nitro group, a carbazole structure, and a group represented by general formula (11)
(III) a nitro group and one or more structures selected from the group consisting of a fluorene structure, a dibenzofuran structure, a dibenzothiophene structure, a naphthalene structure, a diphenylmethane structure, a diphenylamine structure, a diphenylether structure, and a diphenylsulfide structure;

(In general formula (11), X ⁷ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. X ⁷ is a direct bond, an alkylene group having 1 to 10 carbon atoms, or a cycloalkylene group having 4 to 10 carbon atoms, then R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms. , represents an acyl group having 2 to 10 carbon atoms, or a nitro group. X ⁷ is an arylene group having 6 to 15 carbon atoms, R ²⁹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms. , a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. R. ³⁰ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a represents 0 or 1, and b represents an integer of 0-10. ) The (C1-1) oxime ester photopolymerization initiator has a halogen-substituted group,
The negative photosensitive resin composition according to any one of claims 1 to 7 . The (Da) black agent has a maximum transmission wavelength of 330 to 410 nm,
The (C1-1) oxime ester photopolymerization initiator has a maximum absorption wavelength of 330 to 410 nm,
The absorbance at a wavelength of 360 nm in a 0.01 g/L propylene glycol monomethyl ether acetate solution of the oxime ester photopolymerization initiator (C1-1) is 0.20 or more.
The negative photosensitive resin composition according to any one of claims 1 to 8 . The (C1-1) oxime ester photopolymerization initiator has a maximum absorption wavelength of 340 to 400 nm,
The absorbance at a wavelength of 360 nm in a 0.01 g/L propylene glycol monomethyl ether acetate solution of the oxime ester photopolymerization initiator (C1-1) is 0.25 or more.
The negative photosensitive resin composition according to claim 9 . The (A) alkali-soluble resin further comprises (A2-1) a polysiloxane, (A2-2) a polycyclic side chain-containing resin, (A2-3) an acid-modified epoxy resin, and (A2-4) an acrylic resin. (A2) containing a second resin containing one or more types selected from the group consisting of
The negative photosensitive resin composition according to any one of claims 1 to 10 . The (C1-1) oxime ester photopolymerization initiator contains a compound represented by the general formula (13),
The negative photosensitive resin composition according to any one of claims 1 to 11 . The (C1-1) oxime ester photopolymerization initiator contains the compound represented by the general formula (12) and/or the compound represented by the general formula (13),
In the general formula (12) and the general formula (13), Y ¹ and Y ² are each independently carbon or nitrogen, and R ⁴⁶ and R ⁴⁷ are alkenyl having at least 1 to 10 carbon atoms. wherein R ⁴⁹ and R ⁵⁰ comprise an alkenyl group having at least 1 to 10 carbon atoms;
The negative photosensitive resin composition according to any one of claims 1 to 11 . Furthermore, (F) the polyfunctional thiol compound is selected from the group consisting of the compound represented by the general formula (83), the compound represented by the general formula (84), and the compound represented by the general formula (85) containing one or more
The negative photosensitive resin composition according to any one of claims 1 to 13 .

(In general formulas (83) to (85), X ⁴² and X ⁴³ represent a divalent organic group. X ⁴⁴ and X ⁴⁵ each independently represent a direct bond or an alkylene chain having 1 to 10 carbon atoms. Y ⁴² to Y ⁵³ each independently represent a direct bond, an alkylene chain having 1 to 10 carbon atoms or a group represented by general formula (86), and Z ⁴⁰ to Z ⁵¹ each independently represent represents a direct bond or an alkylene chain having 1 to 10 carbon atoms, R ²³¹ to R ²⁴² each independently represents an alkylene chain having 1 to 10 carbon atoms, and ^{R 243} to R ²⁴⁵ each independently represent an alkylene chain having 1 to 10 carbon atoms. , hydrogen or an alkyl group having 1 to 10 carbon atoms, a, b, c, d, e, f, h, i, j, k, w, and x each independently represent 0 or 1 g and l each independently represent an integer of 0 to 10. m, n, o, p, q, r, s, t, u, v, y and z each independently , represents an integer of 0 to 10. α and β each independently represent an integer of 1 to 10.)

(In general formula (86), R ²⁴⁶ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. Z ⁵² represents a group represented by general formula (87) or a group represented by general formula (88). represents an integer of 1 to 10, b represents an integer of 1 to 4, c represents 0 or 1, d represents an integer of 1 to 4, e represents 0 or represents 1. When c is 0, d is 1. In general formula (88), R ²⁴⁷ represents hydrogen or an alkyl group having 1 to 10 carbon atoms.) Furthermore, (B) contains an alicyclic group-containing radically polymerizable compound as (B) a radically polymerizable compound,
(B4) the alicyclic group-containing radically polymerizable compound contains a condensed polycyclic alicyclic skeleton,
The negative photosensitive resin composition according to claim 14 . Furthermore, the (C1) photopolymerization initiator includes (C1-2) an α-aminoketone-based photopolymerization initiator, (C1-3) an acylphosphine oxide-based photopolymerization initiator and (C1-4) a biimidazole-based photopolymerization containing one or more selected from the group consisting of initiators,
The content ratio of the (C1-1) oxime ester photopolymerization initiator in the (C1) photopolymerization initiator is 55 to 95% by mass.
The negative photosensitive resin composition according to any one of claims 1 to 15 . Furthermore, as the (B) radically polymerizable compound, one or more selected from the group consisting of (B1) a fluorene skeleton-containing radically polymerizable compound and/or (B2) an indane skeleton-containing radically polymerizable compound,
The negative photosensitive resin composition according to any one of claims 1 to 16 . Furthermore, (B) contains (B3) a flexible chain-containing aliphatic radically polymerizable compound as a radically polymerizable compound,
(B3) the flexible chain-containing aliphatic radically polymerizable compound has at least one lactone-modified chain and/or at least one lactam-modified chain,
The negative photosensitive resin composition according to any one of claims 1 to 17 . Used to collectively form the stepped shape of the pixel division layer in an organic EL display,
The negative photosensitive resin composition according to any one of claims 1 to 18 . The negative photosensitive resin composition according to any one of claims 1 to 19 is cured,
Hardened film. The optical density per 1 μm of film thickness of the cured film according to claim 20 is 0.3 to 5.0,
The cured film is formed into a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT flattening layer, an electrode flattening layer, a wiring flattening layer, a TFT protective layer, an electrode protective layer, a wiring protective layer and a gate insulating layer. Provided as one or more types selected from the group consisting of
organic EL display. The cured film includes a cured pattern having a step shape,
When the film thickness of the thick film portion is (T _FT ) μm and the film thickness of the thin film portion is (T _HT ) μm in the cured pattern having the stepped shape, the (T _FT ) and the (T _HT ) The film thickness difference (ΔT _FT-HT ) μm is 1.5 to 10.0 μm,
The organic EL display according to claim 21. A method for manufacturing an organic EL display,
A step of forming a coating film of the negative photosensitive resin composition according to any one of claims 1 to 19 on a substrate,
a step of irradiating the coating film of the negative photosensitive resin composition with actinic rays through a photomask;
developing with an alkaline solution to form a pattern of the negative photosensitive resin composition; and heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.
A method for manufacturing an organic EL display. The photomask is a photomask having a pattern including a light-transmitting portion and a light-shielding portion, wherein between the light-transmitting portion and the light-shielding portion, the transmittance is lower than the value of the light-transmitting portion and the light-shielding transmittance. A halftone photomask having a semi-transparent portion higher than the value of the part,
24. The method of manufacturing an organic EL display according to claim 23.

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